Method for manufacturing a three-dimensional object and apparatus for the method

Abstract

To provide a method for the fabrication of a three-dimensional object, and an apparatus for the same method.SOLUTION: There is provided a method and an apparatus comprising a dewetting phase and a polymerization liquid that are immiscible, and can be used for the formation of three-dimensional objects, wherein the method does not require a dead zone. Additionally, a method and an apparatus that employ an optically transparent cooling apparatus to mitigate heat generated during the fabrication process, and the use of a mobile phase to provide a shearing interface to reduce interfacial adhesive forces.SELECTED DRAWING: None

Description

Technical Field

[0001] Description of Government Support This invention was made with government support under grant number FA9550-16-1-0150 from the Air Force Research Laboratory. The government has certain rights in this invention.

[0002] This disclosure generally relates to methods and apparatus for fabricating three-dimensional objects. More specifically, this disclosure relates to methods and apparatus for fabricating three-dimensional objects from polymerizable liquids in a bottom-up manner at solid-liquid, liquid-hydrogel, solid-solid, or solid-hydrogel phase interfaces without the need for dead zones or inhibition layers. This disclosure also relates to the use of optically transparent cooling devices that use a mobile phase to provide a shear interface to reduce interfacial adhesion forces to mitigate heat generated during the fabrication process.

Background Art

[0003] In conventional additive manufacturing techniques or three-dimensional manufacturing techniques, the construction of three-dimensional objects is carried out in a stepwise or alternating layer-by-layer manner. Specifically, layer formation is carried out by solidifying a photocurable resin that has been subjected to the action of visible light irradiation or UV light irradiation. The following two techniques are known. That is, in one, a new layer is formed on the upper surface of the growing object, and in the other, a new layer is formed on the bottom surface of the growing object.

[0004] When forming a new layer on the upper surface of the growing object, after each irradiation step, the object being constructed is lowered into a resin "pool", a new layer of resin is coated on top, and a new irradiation step is performed. An early example of such a technique is shown in FIG. 3 of Hull's U.S. Patent No. 5,236,637. The disadvantages of such "top-down" techniques are that it is necessary to immerse the growing object in a (potentially deep) pool of liquid resin and to reconstruct an accurate coating layer of the liquid resin.

[0005] When forming a new layer at the bottom of a growing object, after each irradiation step, the object under construction must be separated from the bottom plate in the build well. An early example of such a technique is shown in FIG. 4 of Hull's U.S. Patent No. 5,236,637, where a polymerizable liquid is floated on top of a non-wetting immiscible liquid layer. However, such a technique has not been commercialized, and instead, dramatically different techniques for "bottom-up" fabrication have been implemented. For example, in U.S. Patent No. 7,438,846, an elastic separation layer is used to achieve "non-destructive" separation of the solidified material at the bottom build plane. Other approaches, such as the B9Creator™ 3D printer commercially available from B9Creations of Deadwood (South Dakota, USA), induce mechanical cleavage after the layer has solidified using a sliding build plate. See, for example, U.S. Patent Application Publication No. 2013 / 0292862 to M. Joyce and U.S. Patent Application Publication No. 2013 / 0295212 to Y. Chen et al. (both on November 7, 2013). See also Y. Pan et al., J. Manufacturing Sci. and Eng. 134, 051011-1 (October 2012). Such approaches introduce mechanical steps that can complicate the apparatus, be time-consuming in the method, and / or potentially distort the final product.

[0006] Some “bottom-up” fabrication approaches, such as the Carbon3D system, utilize a “dead zone” or “inhibiting layer” where polymerization is chemically suppressed near the build interface. The “dead zone” is created by allowing a polymerization inhibitor, such as oxygen, to pass partially or fully through a semi-permeable membrane, enabling continuous supply of the inhibitor to the “dead zone”. By preventing polymerization at the interface, adhesion is avoided and the solidified material can be continuously withdrawn from the build area. However, this system has several limitations. Specifically, the “dead zone” is very sensitive to temperature, and minor fluctuations can cause print failure. Additionally, the polymerization reaction is highly exothermic, and heat must be dissipated without disturbing the “dead zone”. However, a cooling configuration effective in dissipating excessive heat over a large area (a cooling configuration providing an active cooling mechanism) also inhibits oxygen permeation and the formation of the “dead zone”. As a result, the area of the build region (i.e., the width and height of the plane) is limited to a cooling configuration that does not interfere with oxygen delivery to the “dead zone”.

[0007] Accordingly, there is a need for alternative methods and apparatuses for three-dimensional fabrication that can avoid the need for a mechanical separation step in “bottom-up” fabrication. SUMMARY OF THE INVENTION

[0008] One aspect of the present disclosure provides a method of forming a three-dimensional object, the method comprising providing an adhesion stage and a member, the member having a repellent phase thereon, the repellent phase having a build surface, the adhesion stage and the build surface defining a build region therebetween; providing a polymerizable liquid to the build region, the polymerizable liquid being immiscible with the repellent phase; subjecting the polymerizable liquid to polymerization by exposing the build region to energy through at least a portion of the repellent phase to form a solid polymer from the polymerizable liquid; and advancing the adhesion stage away from the build surface to form a three-dimensional object comprising the solid polymer, wherein the repellent phase is not a liquid.

[0009] Another aspect of the present disclosure provides a method of forming a three-dimensional object, the method comprising providing an adhesion stage, a member, and a cooling device, wherein the member has a repelling phase thereon, the member is between the cooling device and the repelling phase, the repelling phase has a build surface, and the adhesion stage and the build surface define a build region therebetween; providing a polymerizable liquid to the build region, the polymerizable liquid being immiscible with the repelling phase; subjecting the polymerizable ink to polymerization by exposing the build region to energy through at least a portion of the optionally transparent cooling device and through at least a portion of the repelling phase to form a solid polymer from the polymerizable liquid; and advancing the adhesion stage away from the build surface to form a three-dimensional object comprising the solid polymer.

[0010] Another aspect of the present disclosure provides an apparatus for forming a three-dimensional object from a polymerizable liquid, the apparatus comprising a support; an adhesion stage operably associated with the support, on which the three-dimensional object is formed; a member having a repelling phase thereon, the repelling phase having a build surface, the repelling phase not being a liquid, and the build surface and the adhesion stage defining a build region therebetween; a polymerizable liquid supply operably associated with the build for supplying a polymerizable liquid into the build region for solidification or polymerization; an energy source configured to deliver energy through the member to the build region to form a solid polymer from the polymerizable liquid; and at least one controller operably associated with the energy source for delivering energy to the build region, the at least one controller also being operably associated with the adhesion stage to advance the adhesion stage away from the build surface at a rate depending on the energy intensity to form a three-dimensional object from the solid polymer.

[0011] Another aspect of the present disclosure provides an apparatus for forming a three-dimensional object from a polymerizable liquid, comprising a support, an adhesion stage operably associated with the support, on which the three-dimensional object is formed, a member having a repellent phase thereon, the repellent phase having a build surface, the build surface and the adhesion stage defining a build region therebetween, an optically transparent cooling device, a polymerizable liquid supply operably associated with the build surface for supplying the polymerizable liquid into the build region for solidification or polymerization, an energy source configured to deliver energy through the member to form a solid polymer from the polymerizable liquid, at least one controller operably associated with the energy source for delivering energy to the build region, the at least one controller also being operably associated with the cooling device for cooling the build region, and the at least one controller also being operably associated with the adhesion stage for advancing the adhesion stage away from the build surface at a rate dependent on the energy intensity to form a three-dimensional object from the solid polymer.

[0012] Another aspect of the present disclosure provides a method for forming a three-dimensional object, the method comprising providing an adhesion stage and a member, the member having a mobile phase thereon, the mobile phase having a build surface, the adhesion stage and the build surface defining a build region therebetween; providing a polymerizable liquid into the build region, the polymerizable liquid being immiscible with the mobile phase; subjecting the polymerizable liquid to polymerization by exposing the build region to energy through at least a portion of the mobile phase to form a solid polymer from the polymerizable liquid; and advancing the adhesion stage away from the build surface to form a three-dimensional object of solid polymer.

[0013] Another aspect of the present disclosure provides an apparatus for forming a three-dimensional object from a polymerizable liquid, comprising a support, an adhesion stage operably associated with the support on which the three-dimensional object is formed, a member having a layer of a mobile phase thereon, the mobile phase having a build surface, the build surface and the adhesion stage defining a build region therebetween, a polymerizable liquid supply operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization, an energy source configured to deliver energy through the member to form a solid polymer from the polymerizable liquid, and at least one controller operably associated with the energy source for delivering energy to the build region, the at least one controller also being operably associated with the adhesion stage and configured to advance the adhesion stage away from the build surface at a rate that depends on the energy intensity to form a three-dimensional object from the solid polymer.

[0014] For the methods and apparatuses described herein, any features, including but not limited to components, conditions, and steps, are contemplated to be selected from the various aspects, embodiments, and examples provided herein.

[0015] Further aspects and advantages will become apparent to those skilled in the art from a consideration of the following detailed description in conjunction with the drawings. The methods and apparatuses are subject to various forms of embodiments, but the following description describes specific embodiments with the understanding that the present disclosure is illustrative, and is not intended to limit the invention to the specific embodiments described herein.

Brief Description of the Drawings

[0016]

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DETAILED DESCRIPTION OF THE INVENTION

[0017] Methods and apparatuses for forming three-dimensional objects are provided herein. In some embodiments, the method includes providing an adhesion stage and a member, wherein the member has a repellent phase thereon, the repellent phase has a build surface, and the adhesion stage and the build surface define a build region therebetween; providing a polymerizable liquid to the build region, wherein the polymerizable liquid is immiscible with the repellent phase; subjecting the polymerizable liquid to polymerization by exposing the build region to energy through at least a portion of the repellent phase to form a solid polymer from the polymerizable liquid; and advancing the adhesion stage away from the build surface to form a three-dimensional object composed of the solid polymer, wherein the repellent phase is not a liquid. Optionally, the repellent phase is molecularly smooth. Optionally, the method further includes a cooling device arranged to cool the polymerizable liquid in consideration of heat generated by an exothermic polymerization reaction. Optionally, the cooling device is transparent and is provided between an optical engine and the polymerizable liquid across the build region. Optionally, the member is optically transparent. Optionally, the member is not oxygen permeable.

[0018] In some embodiments, the method includes providing an adhesion stage, a member, and a cooling device, wherein the member has a repellent phase thereon, the member is between the cooling device and the repellent phase, the repellent phase has a build surface, and the adhesion stage and the build surface define a build region therebetween; providing a polymerizable liquid to the build region, wherein the polymerizable liquid is immiscible with the repellent phase; subjecting the polymerizable ink to polymerization by exposing the build region to energy through at least a portion of the cooling device and through at least a portion of the repellent phase to form a solid polymer from the polymerizable liquid; and advancing the adhesion stage away from the build surface to form a three-dimensional object composed of the solid polymer. In an embodiment of the foregoing embodiment, the cooling device is optically transparent. Optionally, the member is optically transparent. Optionally, the member is not oxygen permeable.

[0019] In some embodiments, the method comprises providing an adhesion stage and a member, where the member has a moving phase thereon, the moving phase has a build surface, and the adhesion stage and the build surface define a build region therebetween; providing a polymerizable liquid to the build region, where the polymerizable liquid is immiscible with the moving phase; subjecting the polymerizable liquid to polymerization by exposing the build region to energy through at least a portion of the moving phase to form a solid polymer from the polymerizable liquid; and advancing the adhesion stage away from the build surface to form a three-dimensional object comprising the solid polymer. Optionally, the moving phase is recycled through a closed loop. Optionally, the moving phase moves across the member but is not recycled. Optionally, the method further comprises cooling the moving phase. Optionally, the member is optically transparent. Optionally, the member is not oxygen permeable.

[0020] Advancing the adhesion stage away from the build surface includes embodiments where the adhesion stage is mounted on an elevator and moves upward away from a stationary fixed build surface, and / or embodiments where the adhesion stage is fixed and the build surface descends, thereby advancing the adhesion stage away from the build surface. Advancing the adhesion stage away from the build surface further includes moving the adhesion stage toward the build surface, for example, in an oscillatory motion, if the net movement of the adhesion stage is away from the build surface.

[0021] The methods disclosed herein provide, for example, one or more advantages such as providing polymerization directly onto the repelling phase and the surface of the polymerizing liquid, with an adhesion force that is low enough such that mechanical cleavage between each layer of the deposited material is not required. Additionally, by utilizing solid, semi-solid, and gel (e.g., hydrogel) repelling phases, printing can proceed along all direction axes (i.e., is not limited to a horizontal printing plane). Further, as shown in FIG. 4, the interface between the repelling phase and the polymerizing layer enables the system to be actively cooled by a conventional heat exchanger (i.e., one that relies on passive heat diffusion not only at the periphery of the build region but also throughout the build region). Additionally, utilizing a mobile phase provides advantages such as further minimizing the adhesion force between the emerging three-dimensional object and the mobile phase and facilitating replenishment of the polymerizable liquid within the build region. In addition, the use of a mobile phase enables mechanisms for continuous regeneration of the build surface, removal of particulate matter from the mobile phase, and / or direct active cooling.

[0022] Furthermore, by utilizing a low adhesion phase interface, the use of an "inhibitory zone" or "dead zone" where the act of material deposition is suppressed / prevented near the interface is not required. The methods disclosed herein provide an improvement in the efficiency of the hardware required to create the dead zone and the initial time required to establish and stabilize the dead zone. As a result of these advantages (simplified hardware, cooling methods, and build surface regeneration), the methods disclosed herein can create build regions that are much larger than competing techniques.

[0023] Furthermore, as shown in FIG. 5, the phase interface can be used in a Euclidean build space in an omnidirectional manner (e.g., the gel-liquid interface can be horizontal, vertical, or any combination of Euler angles for which printing is desired). Additionally, as shown in FIG. 6, these interfaces can be generated in a curved shape such that they are molecularly smooth but not flat (e.g., generating a gel with a radius of curvature to produce a domed or serpentine build region). As a result, the methods disclosed herein are not limited by the scale, geometric shape, or orientation of the build region.

[0024] Polymerizable liquid

[0025] As used herein, "polymerizable liquid" includes any small building block that binds to form a larger structure, e.g., monomers / oligomers crosslinked by conventional polymer chemistry, small particles / colloidal substances that bind together, metal ions that deposit to form bulk metal, or any other number of chemicals down to microscopic scale building blocks.

[0026] In embodiments, the polymerizable liquid is a state (i.e., phase) of matter distinct from the rejection phase (i.e., a solid rejection phase using a liquid polymerizable liquid, or a fixed bubble rejection phase under a liquid layer of the polymerizable liquid). In embodiments, the polymerizable liquid is a state of matter of the same state as the rejection phase. In embodiments, the polymerizable liquid is a state of matter distinct from the mobile phase. In embodiments, the polymerizable liquid is a state of matter of the same state as the mobile phase. The polymerizable liquid is typically immiscible with the rejection phase and / or the mobile phase.

[0027] In an embodiment, the polymerizable liquid can include a monomer or an oligomer, specifically, a photopolymerizable monomer and / or a free radical polymerizable monomer and oligomer, and a suitable initiator such as a free radical initiator. Examples include, but are not limited to, acrylic, methacrylic, acrylamide, styrene, olefin, halogenated olefin, cyclic alkene, maleic anhydride, alkene, alkyne, carbon monoxide, functionalized oligomer, polyfunctional curing site monomer, functionalized PEG, etc. and combinations thereof. Examples of liquid resins, monomers and initiators include those described in U.S. Patent No. 8,232,043, U.S. Patent No. 8,119,214, U.S. Patent No. 7,935,476, U.S. Patent No. 7,767,728, U.S. Patent No. 7,649,029, International Publication No. 2012 / 129968, Chinese Patent Application Publication No. 102715751, and Japanese Patent Application Laid-Open No. 2012 / 210408, but are not limited thereto.

[0028] In an embodiment, the polymerizable liquid includes an aqueous liquid. In an improved form of the above embodiment, examples of the polymerizable liquid include monomers or oligomers selected from the group consisting of acrylic, methacrylic, urethane, acrylic ester, polyester, cyanoester, acrylamide, maleic anhydride, functionalized PEGs, dimethacrylate oligomers, and combinations thereof.

[0029] In an embodiment, the polymerizable liquid includes an organic liquid. In an improvement of the foregoing embodiment, examples of the polymerizable liquid include monomers or oligomers selected from the group consisting of olefin, halogenated olefin, cyclic alkene, alkene, alkyne, and combinations thereof. In an embodiment, the organic polymerizable liquid is selected from the group consisting of 1,6 - hexanediol diacrylate (HDDA), pentaerythritol triacrylate, trimethylolpropane triacrylate (TMPTA), isobornyl acrylate (IBOA), tripropylene glycol diacrylate (TPGDA), (hydroxyethyl) methacrylate (HEMA), and combinations thereof.

[0030] In the acid-catalyzed polymerizable liquid embodiment, as described above, the polymerizable liquid includes a free-radical polymerizable liquid. However, in other embodiments, the polymerizable liquid includes an acid-catalyzed or cationic polymerization type polymerizable liquid. In such embodiments, examples of the polymerizable liquid include monomers containing groups suitable for acid-catalyzed reactions such as epoxy groups and vinyl ether groups. For this reason, suitable monomers include olefins such as methoxyethene, 4-methoxystyrene, styrene, 2-methylprop-1-ene, 1,3-butadiene, etc., heterocyclic monomers (including lactones, lactams, and cyclic amines), such as oxirane, thietane, tetrahydrofuran, oxazoline, 1,3-dioxepane, oxetan-2-one, etc., and combinations thereof. Examples of suitable (generally ionic or non-ionic) photoacid generators (PAGs) included in the acid-catalyzed polymerizable liquid include onium salts, sulfonium salts, and iodonium salts, such as diphenyliodide hexafluorophosphate, diphenyliodide hexafluoroarsenate, diphenyliodide hexafluoroantimonate, diphenyl p-methoxyphenyl triflate, diphenyl p-toluenyl triflate, diphenyl p-isobutylphenyl triflate, diphenyl p-tert-butylphenyl triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, etc., and mixtures thereof, but are not limited thereto. See, for example, U.S. Patent No. 7,824,839, U.S. Patent No. 7,550,246, U.S. Patent No. 7,534,844, U.S. Patent No. 6,692,891, U.S. Patent No. 5,374,500, and U.S. Patent No. 5,017,461. Also, see Photoacid Generator Selection Guide for the electronics industry and energy curable coatings (BASF 2010).

[0031] In some embodiments of the base-catalyzed polymerizable liquid, the polymerizable liquid comprises a base-catalyzed polymerizable liquid. Suitable base-catalyzed polymerizable liquids include, but are not limited to, malachite green carbinol base that produces hydroxide when irradiated with green light.

[0032] In the hydrogel embodiment, suitable polymerizable liquids include photocurable hydrogels such as poly(ethylene glycol) (PEG) and gelatin. PEG hydrogels are used to deliver various biological agents such as growth factors. However, a major problem faced by PEG hydrogels crosslinked by chain-growth polymerization is the potential for irreversible protein damage. By including affinity-binding peptide sequences into the monomer resin solution prior to photopolymerization, which enables sustained delivery, the maximum release state of biological agents from the photopolymerized PEG diacrylate hydrogel can be enhanced. Gelatin is a biopolymer frequently used in the food, beauty, pharmaceutical, and photographic industries. Gelatin is obtained by thermal denaturation or chemical and physical decomposition of collagen. There are three types of gelatin, including those found in animals, fish, and humans. Gelatin derived from the skin of cold-water fish is considered safe for use in pharmaceutical applications. Appropriately modified gelatin can be crosslinked using UV light or visible light. The method of crosslinking gelatin includes curing derivatives from dyes such as rose bengal.

[0033] Silicone resin Suitable polymerizable liquids include silicone. Silicone can be made photocurable or solidified by a Michael reaction between thiol and vinyl residues using a radical photoinitiator. Suitable photoinitiators include, but are not limited to, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, vinylmethoxysiloxane homopolymer, (mercapto propyl)methylsiloxane homopolymer.

[0034] For biodegradable resins, biodegradable screws and implantable devices such as stents for drug delivery or for temporary applications, biodegradable polymerizable liquids are particularly important (U.S. Patent No. 7,919,162, U.S. Patent No. 6,932,930). A biodegradable copolymer of lactic acid and glycolic acid (PLGA) can be dissolved in dimethacrylic acid PEG to obtain a transparent resin suitable for use. Polycaprolactone and PLGA oligomers can be functionalized with acrylic or methacrylic groups to make them effective resins for use.

[0035] Photocurable polyurethanes A particularly useful polymerizable liquid is a photocurable polyurethane. A photopolymerizable polyurethane composition comprising (1) a polyurethane based on an aliphatic diisocyanate, namely poly(hexamethylene isophthalate glycol) and optionally 1,4-butanediol, (2) a polyfunctional acrylate ester, (3) a photoinitiator, and (4) an antioxidant can be formulated, resulting in a hard, wear-resistant and stain-resistant material (U.S. Patent No. 4,337,130). The photocurable thermoplastic polyurethane elastomer incorporates a photoreactive diacetylene diol as a chain extender.

[0036] High-performance resins In some embodiments, high-performance resins are included as the polymerizable liquid. Sometimes, such high-performance resins may require the use of heat to melt and / or reduce the viscosity of this high-performance resin, as described above and further discussed below. Examples of such resins include, but are not limited to, resin materials for high-performance resins, sometimes referred to as liquid crystal polymers of esters, ester imides and ester amides, as described in U.S. Patent No. 7,507,784, U.S. Patent No. 6,939,940. Since such resins may sometimes be used as thermosetting resins at high temperatures, in the present invention, such resins further include suitable photoinitiators, such as benzophenone initiators, anthraquinone initiators and fluorenone initiators (including their derivatives), to initiate crosslinking by irradiation, as further discussed below.

[0037] Examples of additional resins As polymerizable liquid resins particularly useful for dental applications, EnvisionTEC's Clear Guide and EnvisionTEC's E-Denstone Material can be mentioned. As a resin particularly useful for the hearing aid industry, the resin of EnvisionTEC's e-Shell 300 Series can be mentioned. As a particularly useful resin, EnvisionTEC's HTM140IV High Temperature Mold Material for direct use with vulcanized rubber in molding / casting applications can be mentioned. As a material particularly useful for manufacturing strong and hard parts, EnvisionTEC's RC31 resin can be mentioned. As a resin particularly useful for investment casting applications, EnvisionTEC's Easy Cast EC500 can be mentioned.

[0038] Sol-gel polymerizable liquids In some embodiments, the polymerizable liquid may comprise a sol solution or an acid-catalyzed sol. Such solutions generally include metal alkoxides such as silicon alkoxides such as silicon tetraethoxide (tetraethyl orthosilicate, TEOS) and titanium alkoxides in a suitable solvent. Products with a wide range of different properties can be produced, from rubbery materials (e.g., using silane-terminated silicone rubber oligomers) to very hard materials (glass using only TEOS), and products in the use of combinations of TEOS with various silane-terminated oligomers. Additional components such as dyes and dopants may be included in the sol solution as known in the art, and the firing step after polymerization may also be included as known in the art. See, for example, U.S. Patent No. 4,765,818, U.S. Patent No. 7,709,597, U.S. Patent No. 7,108,947, U.S. Patent No. 8,242,299, U.S. Patent No. 8,147,918, U.S. Patent No. 7,368,514.

[0039] In additional resin component embodiments, the polymerizable liquid includes particulate or colloidal substances that can bond together. In embodiments, the polymerizable liquid includes metal ions that can deposit to form bulk metal. The polymerizable liquid resin or polymerizable material can have solid particles suspended or dispersed therein. Any suitable solid particles can be used depending on the final product being fabricated. The particles can be metal, organic / polymer, inorganic, ceramic, or compositions or mixtures thereof. The particles can be non-conductive, semi-conductive or conductive (including metal conductors and non-metal or polymer conductors), and the particles can be magnetic, ferromagnetic, paramagnetic or non-magnetic. The particles can be of any suitable shape such as spherical, ellipsoidal, cylindrical, etc. The particles can be dissolved and solubilized in the liquid resin as discussed below, and these particles can include active substances. For example, magnetic or paramagnetic particles or nanoparticles can be used.

[0040] The polymerizable liquid can further have additional components solubilized therein, such as pigments, dyes, active compounds or pharmaceutical compounds, detectable compounds (e.g., fluorescent, phosphorescent, radioactive), etc., further depending on the specific purpose of the product being fabricated. Examples of such additional components include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, saccharides, small organic compounds (drugs and drug-like compounds), etc., and combinations thereof.

[0041] The polymerizable liquid can further include one or more additional components dispersed in the polymerizable liquid, including carbon nanotubes, carbon fibers, and glass filaments.

[0042] Polymerizable liquid containing living cells In some embodiments, the polymerizable liquid can hold living cells as "particles" in the polymerizable liquid. Such polymerizable liquids are generally aqueous, can be oxygenated, and can be regarded as "emulsions" in which the living cells are the discontinuous phase. Suitable living cells can be plant cells (e.g., monocotyledonous plants, dicotyledonous plants), animal cells (e.g., mammalian cells, avian cells, amphibian cells, reptilian cells), microbial cells (e.g., prokaryotes, eukaryotes, protozoa, etc.), etc. The cells can be differentiated cells derived from or corresponding to any type of tissue (e.g., blood, cartilage, bone, muscle, endocrine gland, exocrine gland, epithelium, endothelium, etc.), or undifferentiated cells such as stem cells or progenitor cells. In such embodiments, the polymerizable liquid can be one that forms a hydrogel, and examples of the polymerizable liquid include, but are not limited to, those described in U.S. Patent No. 7,651,683, U.S. Patent No. 7,651,682, U.S. Patent No. 7,556,490, U.S. Patent No. 6,602,975, U.S. Patent No. 5,836,313, etc.

[0043] In some embodiments, the polymerizable liquid further comprises a photoinitiator. The photoinitiator used is determined by the wavelength of the light source used. When using a higher energy UV source (i.e., a high-pressure mercury lamp emitting in the region of 200 nm to 400 nm), suitable initiators include 4,4'-bis(diethylamino)benzophenone (trade name Irgacure EMK) having a primary absorbance at about 370 nm, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (trade name Irgacure 819) having a primary absorbance at about 300 nm and a secondary absorbance at 370 nm, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (trade name Duracure TPO) having a primary absorbance at about 380 nm along with secondary absorbances at 370 nm and 390 nm, and bis(2,6-difluoro-3-(1-hydroxypyrrol-1-yl))phenyl)titanocene (trademark name Irgacure 784, Omnicure 784) having a primary absorbance at 300 nm along with strong secondary absorbances at 398 nm and 470 nm, but not limited thereto. See also Photoinitiators for UV Curing Key Products Selection Guide 2003 (Ciba Specialty Chemicals 2003).

[0044] In an embodiment, the photoinitiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. Without intending to be bound by theory, it is believed that despite the low solubility of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, at a concentration of 0.5% by weight, it can be the most versatile initiator due to its overall absorption coefficient and active wavelength. Further, due to its secondary absorbance at 370 nm (wide enough to extend into the visible region), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide can be easily polymerized via a UV source (mercury lamp), a UV blue LED (about 405 nm), a standard off-the-shelf DLP computer projector, and an ambient fluorescent lamp.

[0045] Furthermore, due to its secondary absorbance at 370 nm (wide enough to extend into the visible region), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide can be readily polymerized via a UV source (mercury lamp), a UV blue LED (about 405 nm), a standard off-the-shelf DLP computer projector, and ambient fluorescent lights.

[0046] In some embodiments, the photoinitiator is bis(2,6-difluoro-3-(1-hydroxypyrrol-1-yl)phenyl)titanocene (trade name Irgacure 784, Omnicure 784) having a primary absorbance at 300 nm with strong secondary absorbances at 398 nm and 470 nm. Without being bound by theory, bis(2,6-difluoro-3-(1-hydroxypyrrol-1-yl)phenyl)titanocene enables the polymerizable liquid to be cured using visible light (blue to green light sources) and a number of other light sources such as commercially available LCD displays with LED backlights.

[0047] In some embodiments, the polymerizable liquid further comprises a surfactant. The surfactant can be included in the polymerizable liquid to reduce the interfacial surface tension between the polymerizable liquid and the repellent phase and / or the mobile phase. Exemplary surfactants include, but are not limited to, partially fluorinated acrylic polymers such as Capstone FS-22 and Capstone FS-83 from DuPont (Wilmington, DE), ionic surfactants including CTAB (hexadecyltrimethylammonium bromide), CPC (cetylpyridinium chloride), DOAB (dimethyldioctadecylammonium bromide), SDS (sodium dodecyl sulfate), SDBS (sodium dodecylbenzenesulfonate), non-ionic surfactants including hexaethylene glycol mono-n-dodecyl ether (C12EO6), polyoxyethylene(2)sorbitan monolaurate (Tween-20, polysorbate 20), and tyloxapol.

[0048] Mobile phase

[0049] The mobile phase is immiscible and / or insoluble with the polymerizable liquid and can be any material that moves during polymerization. In some embodiments, the mobile phase is the repellent phase as described herein. The movement of the mobile phase can be described in relation to the emerging object containing the solidified polymer material and / or in relation to the energy source that causes the polymerization liquid to solidify. In some embodiments, the mobile phase moves in a plane and the emerging object and / or the energy source are substantially perpendicular to the plane (e.g., the mobile phase moves in one direction perpendicular to the advancement of the adhesive stage, or the mobile phase rotates and moves perpendicular to the advancement of the adhesive stage). In some embodiments, the mobile phase moves in a plane, the emerging object and / or the energy source are substantially perpendicular to the plane, and the emerging object and the energy source are also moving (e.g., the emerging object and the light engine rotate about a common axis, the mobile phase moves laterally with respect to the object, and the axis of rotation is perpendicular to the mobile phase plane).

[0050] In embodiments, the mobile phase includes a moving solid phase, a moving gel phase, a flowing fluid, or a combination thereof. In some cases, the mobile phase includes a moving solid. In some cases, the mobile phase includes a moving gel. In some cases, the mobile phase includes a flowing fluid. In some cases, the mobile phase includes a combination of a moving solid phase and a flowing liquid.

[0051] The mobile phase can include a moving solid phase selected from the group consisting of organic solids, aqueous solids, perfluorinated solids, and combinations thereof. The organic solids can include, but are not limited to, squalane, squalene, solid hexadecane, and combinations thereof. The aqueous solids can include, but are not limited to, ice, solid tetraethylene glycol, solid PEG-300 (i.e., polyethylene glycol having a molecular weight of 300 Da), solid PEG-400, solid PEG-600, solid high molecular weight PEG, and combinations thereof. The perfluorinated solids can include, but are not limited to, fluorinated ethylene propylene, polytetrafluoroethylene, and combinations thereof. The solid mobile phase can move relative to the objects that appear, for example, by using a conveyor.

[0052] The mobile phase can include a moving gel phase selected from the group consisting of organic gels, silicone gels, aqueous hydrogels, fluorogels, and combinations thereof. The aqueous hydrogels can include, but are not limited to, agar, agarose gel, polyacrylamide gel, starch gel, cationic gel, anionic gel, and combinations thereof. The fluorogels can include, but are not limited to, 2-(perfluorohexyl)ethyl acrylate swollen with perfluoropolyether.

[0053] The mobile phase can include a flowing fluid. Examples of the flowing fluid include aqueous liquids, organic liquids, silicone liquids, and fluorine liquids. The aqueous liquids can include, but are not limited to, water, deuterium oxide, concentrated salt solutions, concentrated sugar solutions, and combinations thereof. Exemplary salts and the solubility limits of the salts in water at about room temperature are as follows: NaCl 35.9 g / 100 ml, NaBr 90.5 g / 100 ml, KBr 67.8 g / 100 ml, MgBr 2 102 g / 100 ml, MgCl 2 54.3 g / 100 ml, sodium acetate 46.4 g / 100 ml, sodium nitrate 91.2 g / 100 ml, CaBr 2143 g / 100 ml, CaCl 2 74.5 g / 100 ml, Na 2 CO 3 21.5 g / 100 ml, NH 4 Br 78.3 g / 100 ml, LiBr 166.7 g / 100 ml, KI 34.0 g / 100 ml, and NaOH 109 g / 100 ml. Thus, for example, 100 ml of a solution of 35.9 g of NaCl has a density of 1204 kg / m 3 Examples of exemplary sugars and their solubility limits in water at about room temperature include sucrose 200 g / ml, maltose 108 g / 100 ml, and glucose 90 g / 100 ml. Thus, for example, a 60% aqueous sucrose solution has a density of 1290 kg / m 3 at room temperature. The silicone liquid can include, but is not limited to, silicone oil. Silicone oil is a liquid polymeric siloxane having organic side chains. Examples of silicone oil include polydimethylsiloxane (PDMS), simethicone, and cyclopolysiloxane. The fluorine liquid can include, but is not limited to, fluorinated oil. Fluorinated oil generally includes liquid perfluorinated organic compounds. Examples of fluorinated oil include perfluoro-n-alkane, perfluoropolyether, perfluoroalkyl ether, copolymers of substantially fluorinated molecules, and combinations thereof. The organic liquid can include, but is not limited to, organic oil, chlorinated solvents (e.g., dichloromethane, dichloroethane, and chloroform), and organic solvents that are immiscible with aqueous systems. Organic oil is a viscous liquid at ambient temperature and includes neutral nonpolar organic compounds that are both hydrophobic and lipophilic. Examples of organic oil include, but are not limited to, high-density hydrocarbon liquids. In an embodiment, the mobile phase includes a silicone liquid, a fluorine liquid, or a combination thereof.

[0054] The flow of the mobile phase can be at a rate that remains in a laminar flow state to avoid interface turbulence while generating a shear flow profile between the polymerizable liquid phase and the mobile phase. When the mobile phase is a flowing fluid, the generation of the laminar profile can be facilitated by using a distribution nozzle that produces a series of equally spaced outlets for the homogenous mobile phase, with the inlet forming a single high-flow inlet and outlet (e.g., as shown in FIG. 13).

[0055] In some cases, the mobile phase can be recycled in a closed loop. In some cases, the mobile phase moves from a first mobile phase supply reservoir to a second mobile phase capture reservoir and is not recycled through a closed loop. The mobile phase can be collected from the second reservoir and optionally filtered, washed, and / or decontaminated and returned to the first supply reservoir for reuse. The mobile phase can be collected from the second reservoir and optionally filtered, washed, and / or decontaminated, and the flow direction can be reversed to return the mobile phase to the first reservoir.

[0056] Optionally, the mobile phase is optically transparent. As used herein, unless otherwise specified, "optically transparent" means that an optically transparent element enables a transmittance of an energy event that initiates the solidification of the polymerizable liquid from 1% to 100%. In some cases, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90% of the energy event passes through the optically transparent element. The optically transparent element can enable the transmission of a wide range of wavelengths including, but not limited to, wavelengths corresponding to X-ray radiation, ultraviolet (UV) light radiation, visible light radiation, infrared (IR) radiation, and microwave radiation.

[0057] The mobile phase can further contain a surfactant. The surfactant can be included in the mobile phase to reduce the interfacial surface tension between the polymerizable liquid and the mobile phase. Exemplary surfactants include, but are not limited to, partially fluorinated acrylic polymers (such as Capstone FS-22 and Capstone FS-83 from DuPont (Wilmington, DE)), CTAB (hexadecyltrimethylammonium bromide), CPC (cetylpyridinium chloride), DOAB (dimethyldioctadecylammonium bromide), SDS (sodium dodecyl sulfate), SDBS (sodium dodecylbenzenesulfonate) and other ionic surfactants, non-ionic surfactants including, but not limited to, hexaethylene glycol mono-n-dodecyl ether (C12EO6), polyoxyethylene (2) sorbitan monolaurate (Tween-20, polysorbate 20), and tyloxapol and other non-limiting examples.

[0058] Repellent phase

[0059] Aspects of the methods disclosed herein rely on the use of a phase boundary as a build region that can be molecularly smooth due to the interfacial surface tension of the repellent phase and the polymeric liquid that together constitute the interface system. The repellent phase and the polymeric liquid are generally immiscible. In embodiments, the repellent phase and the polymeric liquid are "repellent" such that polymerization can occur without a strong adhesive force between the solidified polymer and the underlying phase. In embodiments, the repellent phase can be a mobile phase, enabling polymerization to occur without a strong adhesive force between the solidified polymer and the underlying phase. As a result of these small forces, the solidified "printed" material can be easily lifted from the surface in a continuous manner. In embodiments, when the polymeric liquid and / or the repellent phase are substantially free of surfactants, the repellent phase and the polymeric liquid have a contact angle greater than 60° or greater than 90°. In some embodiments, when the polymeric liquid is substantially free of surfactants, the repellent phase and the polymeric liquid phase have a contact angle greater than 60°. As used herein, unless otherwise specified, "substantially free of surfactants" refers to a surfactant concentration of less than about 500 ppm, less than about 250 ppm, less than about 100 ppm, or less than about 50 ppm, or about 10 ppm.

[0060] As used herein, "repellency" means that the phases repel each other and have a contact angle θ greater than 60° or a contact angle θ greater than 90°. A contact angle of 0° indicates complete wettability, a contact angle between 0° and 90° generally indicates high wetting properties, a contact angle between 90° and 180° generally indicates low wetting properties, and a contact angle of 180° indicates complete non-wetting properties. It is not necessary to achieve complete repellency, and in some cases, a combination of lower wettability may be satisfactory. However, the contact angle between the polymerizable liquid and the repellent phase during the polymerization process is generally preferably such that a repellent phase greater than 60° is achieved. If such repellency is not essentially achieved by a specific combination of the polymerizable liquid and the repellent phase, the wettability between the two liquids can be reduced by the inclusion of one or more surfactants, co-solvents, pH, or temperature so as to change the surface tension of the polymerizable liquid and the contact angle at the phase interface. It should be noted that the contact angle is generally defined for a solid-liquid-gas interface. Thus, wetting is usually defined for a combination of solid, liquid, and gas (when the gas phase is not specified, it is considered to be air at standard temperature and pressure). Further, it should be noted that just because a phase is solid does not necessarily mean that the phase supports the weight of the second phase and may be deformed as a result of that weight. For example, considering the configuration shown in FIG. 8, if the bottom phase is not a rigid solid, β does not have to be 180°. As a result, in contrast to θ, it is easier to define three phase interfaces for α. When β is not equal to 180°, the repellent interface is less dependent on the deformation of the β phase, so the repellent interface can be defined as the interface where the value of α is less than 90°.

[0061] Furthermore, the angle of the contact surface can be defined between two liquids on a solid interface (e.g., a droplet in a liquid), as is often the case when viewing the immersed surface. As a result, the contact angle is described with respect to all three phases (the chloroform droplet phase on the surface immersed in water).

[0062] Although not intended to be bound by theory, in embodiments where the reject phase is the mobile phase, when the reject phase and the polymerizable liquid are substantially free of surfactant, the flow of the reject phase provides a lower adhesion force, so the reject phase and the polymerizable liquid can have higher wetting properties (e.g., a contact angle of less than about 90°, e.g., 60°), thereby compensating for higher wettability.

[0063] The method of the present disclosure allows polymerization to occur without a strong adhesive force between the solidified polymer and the underlying reject and / or mobile phase, so the polymerizable liquid does not require a dead zone or an inhibition zone. Thus, in embodiments, the polymerizable liquid is free of a dead zone. Further, since the method of the present disclosure can use a reject phase that is not a liquid, the interface can be advantageously used in an all-directional manner and / or the interface can be formed in a curved shape so as to be molecularly smooth but not flat. Thus, in embodiments, the reject phase is curved. In embodiments, the build surface is not textured.

[0064] In embodiments, the reject phase includes a gel. In embodiments, the reject phase is a gel selected from the group consisting of organic gels, silicone gels, aqueous hydrogels, fluorogels, and combinations thereof. In an improved form of the foregoing embodiments, the reject phase is an aqueous hydrogel, and the aqueous hydrogel is selected from the group consisting of agar, agarose gel, polyacrylamide gel, starch gel, cationic gel, anionic gel, and combinations thereof. In an improved form, the reject phase is a fluorogel, and the fluorogel contains 2-(perfluorohexyl)ethyl acrylate swollen with perfluoropolyether.

[0065] In an embodiment, the rejection phase includes a solid. In an embodiment, the rejection phase is a solid, and the solid is selected from the group consisting of an organic solid, an aqueous solid, a perfluorinated solid, and combinations thereof. In an improved form of the foregoing embodiment, the rejection phase is an organic solid, and the organic solid is selected from the group consisting of squalane, squalene, solid hexadecane, and combinations thereof. In the improved form, the rejection phase is an aqueous solid, and the aqueous solid is selected from the group consisting of ice, solid tetraethylene glycol, solid PEG-300, solid PEG-400, solid PEG-600, and combinations thereof. In the improved form, the rejection phase is a perfluorinated solid, and the perfluorinated solid includes a solid perfluoropolyether.

[0066] In an embodiment, the rejection phase includes a gas.

[0067] In an embodiment, the rejection phase includes a liquid. The liquid rejection phase can include an aqueous liquid, an organic liquid, a silicone liquid, a fluorine liquid, and combinations thereof. In an embodiment, the liquid rejection phase includes a silicone liquid, a fluorinated liquid, or a combination thereof. The fluorinated liquid can include, but is not limited to, perfluoro-n-alkane, perfluoropolyether, perfluoroalkyl ether, a copolymer of substantially fluorinated molecules, and combinations thereof.

[0068] In some embodiments, the rejection phase further includes a surfactant. The surfactant may be included in the rejection phase to reduce the interfacial surface tension between the polymerizable liquid and the rejection phase. Exemplary surfactants include, but are not limited to, partially fluorinated acrylic polymers (such as Capstone FS-22 and Capstone FS-83 from DuPont (Wilmington, DE)), CTAB (hexadecyltrimethylammonium bromide), CPC (cetylpyridinium chloride), DOAB (dimethyldioctadecylammonium bromide), SDS (sodium dodecyl sulfate), SDBS (sodium dodecylbenzenesulfonate), and other ionic surfactants, non-ionic surfactants including hexaethylene glycol mono-n-dodecyl ether (C12EO6), polyoxyethylene (2) sorbitan monolaurate (Tween-20, polysorbate 20), and tyloxapol, among others.

[0069] In an embodiment, the rejection phase is optically transparent.

[0070] Polymerization initiator / energy source

[0071] To fabricate a three-dimensional object from the polymerizable liquid, an initiating event that induces solidification or deposition from the polymerizable liquid is required. Deposition can be, for example, photoactivation, electroactivation, thermal activation, and / or magnetic activation. In an embodiment, the polymerization is carried out by electromagnetic irradiation. In an embodiment, the polymerization is carried out by electricity. In an embodiment, the polymerization is carried out by thermal activation. In an embodiment, the polymerization is carried out by magnetic activation.

[0072] In an embodiment, the method is carried out in parallel using a multi-chip array, and the chips of the multi-chip array include members. The multi-chip array can be by a beam pen lithography system and / or a polymer pen lithography system. A schematic diagram of these embodiments is shown in FIG. 7.

[0073] In an embodiment, beam pen lithography has a multi-chip array as part of a beam pen lithography system. Beam pen lithography (BPL) is described, for example, in U.S. Patent No. 9,021,611, which is hereby incorporated by reference in its entirety. BPL can enable patterning of submicron features over large areas with flexible pattern design, convenient and selective pen tip addressability, and low fabrication costs. Compared to conventional photolithography or contact printing, which can only replicate pre-formed patterns (i.e., photomasks), BPL can provide flexibility in generating different patterns by controlling the movement of the chip array on the substrate and / or selectively irradiating one or more of the pen tips of the chip array (e.g., enabling selective passage of energy through one or more of the pen tips of the chip array to initiate polymerization of a polymerizable liquid). Thus, for example, multiple objects can be fabricated in parallel.

[0074] The BPL chip array includes a chip substrate layer and a plurality of chips fixed to the chip substrate layer. The chip substrate layer and the plurality of chips are formed of a transparent polymer. The chip substrate layer and the chips can be formed from the same polymer or from different polymers. The chip array further includes a blocking layer coated on the sidewalls of the chips and on portions of the chip substrate layer between adjacent chips. Openings are defined in the blocking layer at the chip ends (e.g., at the photosensitive layer contact ends of each chip), such that the transparent polymer chip ends are exposed through the openings.

[0075] The chip substrate layer can be attached, for example, to a transparent (e.g., optically transparent) rigid support formed from glass, silicon, quartz, ceramic, polymer, or any combination thereof. The rigid support preferably has a very high rigidity and a very flat surface for mounting the chip array.

[0076] The chip array is non-cantilevered and includes chips, which can be designed to have any shape or spacing (pitch) between the chips as required. The shape of each chip may be the same as or different from the other chips in the array, and preferably, the chips have a common shape. Intended chip shapes include ellipsoids of revolution, hemispherical ellipsoids, toroids, polyhedra, cones, cylinders, and pyramids (triangular or square). The chips have a base fixed to the chip substrate layer. The base is preferably larger than the chip end. The base can have an edge length in the range of about 1 μm to about 50 μm, or about 5 μm to about 50 μm. A preferred chip array preferably includes thousands of chips having a pyramid shape. The substrate contact (chip end) portion of each chip can have a diameter in the range of about 50 nm to about 1 μm. The substrate contact portion of the chips is preferably sharp for each to be suitable for forming, for example, a sub-micron pattern of less than about 500 nm. The sharpness of the chip is measured by its radius of curvature. The chip can have, for example, a radius of curvature of less than about 1 μm. The spacing (chip pitch) between adjacent chips can range from about 1 μm to more than about 10 mm.

[0077] The blocking layer on the sidewall of the polymer chip acts as a radiation blocking layer, ensuring that radiation is incident on the surface of the substrate layer on the side opposite to the surface where the chip is fixed such that the radiation is irradiated only through the chip end portion exposed by the opening defined in the blocking layer. By exposing the substrate pre-coated with a resist layer to the radiation guided through the chip end portions of the chip array, polymerization of the polymerizable liquid at each chip end portion can be enabled. The blocking layer can be formed of any material suitable for blocking (e.g., reflecting) radiation of the type used in a lithography process. For example, when used with UV light, the blocking layer can be a metal such as gold. Other suitable blocking layers include, but are not limited to, gold, chromium, titanium, silver, copper, nickel, silicon, aluminum, opaque organic molecules, and polymers, as well as combinations thereof. The blocking layer can have any suitable thickness, for example, in the range of about 40 nm to about 500 nm.

[0078] Polymer materials suitable for use in a chip array can have a linear or branched backbone and may or may not be cross-linked depending on the desired degree of compressibility for the appropriate polymer and chip. A cross-linking agent means a polyfunctional monomer capable of forming two or more covalent bonds between polymer molecules. Non-limiting examples of cross-linking agents include trimethylolpropane trimethacrylate (TMPTMA), divinylbenzene, diepoxide, triepoxide, tetraepoxide, divinyl ether, trivinyl ether, tetravinyl ether, and combinations thereof.

[0079] A thermoplastic or thermosetting polymer can be used, which may be a cross-linked elastomer. Generally, the polymer can be porous and / or amorphous. Various elastic polymer materials are contemplated, including polymers of common silicone polymer groups and epoxy polymer groups. Polymers having a low glass transition temperature, for example, a glass transition temperature of less than 25 °C or more preferably less than -50 °C, can be used. In addition to aromatic amines, triazines, and compounds mainly composed of an alicyclic skeleton, diglycidyl ether of bisphenol A can be used. As another example, novolak polymers can be mentioned. Other elastomeric polymers contemplated include methylchlorosilane, ethylchlorosilane, and phenylchlorosilane, polydimethylsiloxane (PDMS). Other materials include polyethylene, polystyrene, polybutadiene, polyurethane, polyisoprene, polyacrylic rubber, fluorosilicone rubber, and fluoroelastomer.

[0080] Further examples of suitable polymers that can be used to form the chip can be found in U.S. Patent No. 5,776,748, U.S. Patent No. 6,596,346, and U.S. Patent No. 6,500,549, each of which is incorporated herein by reference in its entirety. Other suitable polymers include those disclosed by He et al. in Langmuir 2003, 19, 6982-6986, Donzel et al. in Adv. Mater. 2001, 13, 1164-1167, and Martin et al. in Langmuir, 1998, 14-15, 3791-3795. Hydrophobic polymers, such as polydimethylsiloxane, can be chemically or physically modified, for example, by exposure to a solution of a strong oxidizing agent or an oxygen plasma.

[0081] The polymer of the chip array can be a polymer gel. The gel polymer can include any suitable gel including hydrogels and organic gels. For example, the polymer gel can be a silicone hydrogel, a branched polysaccharide gel, an unbranched polysaccharide gel, a polyacrylamide gel, a polyethylene oxide gel, a crosslinked polyethylene oxide gel, a poly(2-acrylamido-2-methyl-1-(polyAMPS) gel, a polyvinylpyrrolidone gel, a crosslinked polyvinylpyrrolidone gel, a methylcellulose gel, a hyaluronan gel, and combinations thereof. For example, the polymer gel can be an agarose gel. By weight, most of the gel is liquid. For example, the gel can be a liquid greater than 95%, but because there is a crosslinked network in the liquid, it behaves like a solid.

[0082] The material used to form the chip array has a compressive modulus and surface hardness suitable for preventing the crushing of the chips during contact with the surface, but an overly high modulus and overly large surface hardness can result in a brittle material that cannot adapt and conform to the substrate surface during exposure. As disclosed in Macromolecules by Schmid et al., 33:3042 (2000), vinyl and hydrosilane prepolymers can be adjusted to provide polymers with different moduli and surface hardnesses. Thus, in another type of embodiment, the polymer is a mixture of a vinyl and a hydrosilane prepolymer, where the weight ratio of vinyl prepolymer to hydrosilane crosslinking agent is from about 5:1 to about 20:1.

[0083] The chip array and / or build region can move during patterning to form a desired object. For example, in one embodiment, the chip array moves while the build region is stationary. In another embodiment, the chip array is held stationary while the build region moves. In yet another embodiment, both the chip array and the build region move.

[0084] Large-scale 2D array of BPL chips (1 cm 2When using 15,000 pens per hit, very high throughput lithography can be performed using BPL, and thousands of parallel generated 3D objects can be obtained at once. The objects can be made identical, for example, by using a uniform chip array. In an alternative form, at least some of the objects can be different from each other, for example, by using a non-uniformly masked chip array and a lateral displacement of the chip array during printing that exceeds the chip pitch dimension.

[0085] Another factor contributing to the resolution of BPL is the chip aperture size that controls the area exposed to light from the chip. Under UV light sources or halogen light sources and conventional photolithography conditions, objects close to or below the optical diffraction limit of about 200 nm can be generated.

[0086] By moving the surface array while irradiating the chip array from the back of the chip, for example, through the chip substrate layer, an array of large objects can be fabricated simultaneously. The radiation can be maintained throughout the process.

[0087] Individual chips in the BPL array can be addressed by selective irradiation. For example, a number less than all of the chips in the array, such as one or a selected plurality of chips in the chip array, can be irradiated. Selective irradiation of the chips can be achieved, for example, by selectively focusing light through the base of each chip. The chip array can also include one or more spatial light modulators that can block specific chips from exposure to light. The spatial light modulator can be controllable statically and / or dynamically. For example, the spatial light modulator can be a shutter. The spatial light modulator can be formed using various materials including, for example, liquid crystals. The spatial light modulator can be a mask that is not dynamically controllable, for example. The spatial light modulator can be arranged or formed as part of the chip substrate layer.

[0088] In an embodiment, in polymer pen lithography, a multi-chip array is part of a polymer pen lithography system. Polymer pen lithography is a direct writing method that releases a collection of molecules in a positive printing mode. Polymer pen lithography utilizes an elastomeric chip without a cantilever. The chip is preferably made of polydimethylsiloxane (PDMS). A preferred polymer pen array preferably includes thousands of chips in a pyramid shape, and this pen array can be fabricated using a master prepared by conventional photolithography and subsequent wet chemical etching. The chips are connected, for example, by a common substrate including a thin polymer backing layer (50 - 100 μm thick) that is adhered to a rigid support (e.g., glass, silicon, quartz, ceramics, polymer, or any combination thereof), preferably before or through the curing of the polymer. The rigid support preferably has a highly rigid and highly flat surface on which an array (e.g., silica glass, quartz, etc.) is mounted. The rigid support and the thin backing layer significantly improve the uniformity of the polymer pen array over a large area, such as the surface of a 3-inch wafer, enabling this planarization and enabling uniform and controlled use of the array. The polymer pen chip array is disclosed, for example, in International Publication No. WO 2009 / 132321, the disclosure of which is hereby incorporated by reference in its entirety.

[0089] In an embodiment, one or more of the array chip, the backing layer, and the rigid support are at least translucent, preferably transparent.

[0090] The chip array is non-cantilevered and includes chips that can be designed to have any shape or spacing between chips, as required. The shape of each chip may be the same as or different from the other chips in the array. Intended chip shapes include ellipsoids of revolution, hemispherical ellipsoids, toroids, polyhedra, cones, cylinders, and pyramids (triangular or square). The sharpness of the chips is measured by their radius of curvature, and the radius of curvature of the chips disclosed herein is less than 1 μm. The chip array can be formed from a mold made using photolithography, and then this mold can be used to manufacture the chip array using a polymer as disclosed herein. The mold can be processed to include many chips aligned in any desired manner. The number of chips in the chip array can be any desired number, and the intended number of chips includes from about 1,000 chips to about 15,000,000 chips, or more.

[0091] The polymer can be any polymer having a compressibility suitable for lithography. Polymer materials suitable for use in the chip array can have a linear or branched backbone and may or may not be cross-linked depending on the degree of compressibility desired for the appropriate polymer and chip. A cross-linking agent means a polyfunctional monomer capable of forming two or more covalent bonds between polymer molecules. Non-limiting examples of cross-linking agents include trimethylolpropane trimethacrylate (TMPTMA), divinylbenzene, diepoxides, triepoxides, tetraepoxides, divinyl ethers, trivinyl ethers, tetravinyl ethers, and combinations thereof.

[0092] A thermoplastic or thermosetting polymer can be used, which may be a cross-linked elastomer. Generally, the polymer can be porous and / or amorphous. Various elastic polymer materials are contemplated, including polymers of common silicone polymer groups and epoxy polymer groups. Polymers having a low glass transition temperature, for example less than 25 °C or more preferably less than -50 °C, can be used. In addition to aromatic amines, triazines, and compounds mainly composed of alicyclic skeletons, diglycidyl ether of bisphenol A can be used. Another example is novolak polymers. Other elastomeric polymers contemplated include methylchlorosilane, ethylchlorosilane, and phenylchlorosilane, polydimethylsiloxane (PDMS). Other materials include polyethylene, polystyrene, polybutadiene, polyurethane, polyisoprene, polyacrylic rubber, fluorosilicone rubber, and fluoroelastomers.

[0093] Further examples of suitable polymers that can be used to form the chip can be found in U.S. Patent No. 5,776,748, U.S. Patent No. 6,596,346, and U.S. Patent No. 6,500,549, each of which is incorporated herein by reference in its entirety. Other suitable polymers include those disclosed by He et al., Langmuir 2003, 19, 6982 - 6986, Donzel et al., Adv. Mater. 2001, 13, 1164 - 1167, and Martin et al., Langmuir, 1998, 14 - 15, 3791 - 3795. Hydrophobic polymers, such as polydimethylsiloxane, can be chemically or physically modified, for example, by exposure to a solution of a strong oxidizing agent or oxygen plasma.

[0094] The materials used to form the chip array have a compressive modulus of elasticity and surface hardness suitable for preventing the crushing of the chips during contact with the surface. However, an overly high modulus of elasticity and an overly large surface hardness can result in a brittle material that cannot adapt and conform to the substrate surface during exposure. As disclosed in Macromolecules by Schmid et al., 33:3042 (2000), vinyl and hydrosilane prepolymers can be adjusted to provide polymers with different moduli of elasticity and surface hardness. Thus, in another type of embodiment, the polymer is a mixture of a vinyl and a hydrosilane prepolymer, where the weight ratio of the vinyl prepolymer to the hydrosilane crosslinking agent is from about 5:1 to about 20:1.

[0095] The material used to form the chip array will preferably have a surface hardness of about 0.2% to about 3.5% of glass, which is measured as the resistance of the surface to the penetration of a 1 mm diameter hard sphere and is compared to the resistance of the glass surface (as described in Macromolecules by Schmid et al., 33:3042 (2000), p3044). The surface hardness can optionally be about 0.3% to about 3.3%, about 0.4% to about 3.2%, about 0.5% to about 3.0%, or about 0.7% to about 2.7% of glass. The polymer of the chip array can have a compressive modulus of elasticity of about 10 MPa to about 300 MPa. The chip array preferably includes a compressible polymer having a Hookean modulus of elasticity under a pressure of about 10 MPa to about 300 MPa. The linear relationship between the pressure exerted on the chip array and the physical size enables the control of the near field and the physical size using the disclosed method and chip array.

[0096] The chip array can be fixed to a common substrate and include a plurality of chips formed from the polymers disclosed herein. The chips can be arranged randomly or in a regular periodic pattern shape (e.g., row and column patterns, circular patterns, etc.). The chips can all have the same shape or can be constructed to have different shapes. The common substrate can include an elastomer layer, and this elastomer layer can include the same polymer as the polymer forming the chips of the chip array or can include a different elastic polymer from that of the chip array. The elastomer layer can have a thickness of about 50 μm to about 100 μm. The chip array can be attached or adhered to a rigid support (e.g., glass, such as a glass slide). In various cases, the common substrate, the chip array, and / or the rigid support, if present, are translucent or transparent. In certain cases, each is translucent or transparent.

[0097] Method for forming a 3D object

[0098] In embodiments, when the polymerizable liquid and the repelling phase are supplied together in a suitable apparatus, the fabrication of a three-dimensional object can be initiated, for example, as shown in FIGS. 1-3. In embodiments, when the polymerizable liquid and the mobile phase are supplied together in a suitable apparatus, the fabrication of a three-dimensional object can be initiated, for example, as shown in FIGS. 9-11. The fabrication can be performed layer by layer or continuously.

[0099] In some embodiments, the advancing step is performed sequentially with a constant increment (e.g., 0.1 or 1 micron to 10 or 100 microns or more) for each step or increment amount. In some embodiments, the advancing step is performed sequentially with a variable increment amount (e.g., each increment in the range of 0.1 or 1 micron to 10 or 100 microns or more) for each step or increment amount. The magnitude of the increment amount, together with the advancing speed, will be determined according to factors such as temperature, pressure, the structure of the article to be manufactured (e.g., size, density, complexity, composition, etc.).

[0100] In other embodiments of the present invention, the advancing step is performed continuously at a constant speed or at a variable speed. Note that even when the advancing step is performed progressively, the production of the product can be continuous (not layer by layer).

[0101] In some embodiments, the speed of advancement (performed either sequentially or continuously), is, again for example, from about 0.1, 1 or 10 microns per second to about 100, 1,000 or 10,000 microns per second, depending on factors such as temperature, pressure, the structure of the article being manufactured, the intensity of irradiation, etc. In an embodiment, by an arm that maintains the adhesion stage, the print is withdrawn from the build surface at a constant speed from about 10 microns per second, or from about 30 microns per second to about 200 microns, about 180 microns, about 160 microns, about 140 microns, or up to about 120 microns per second, thereby advancing the adhesion stage away from the build surface at a constant speed from about 10 microns per second to about 200 microns per second. In an embodiment, the print withdraws from the build surface at a speed in the range from about 100 microns per second to about 140 microns per second, for example 120 microns per second.

[0102] Advancing the adhesion stage away from the build surface can include advancing the adhesion stage a fixed distance away from the build surface at a constant speed, then pausing for a fixed time, and optionally repeating. Advancing the adhesion stage away from the build surface can include advancing the adhesion stage a fixed distance away from the build surface at a variable speed, then pausing for a fixed time, and optionally repeating. A cycle of advancing the adhesion stage a fixed distance away from the build surface and then pausing for a fixed amount of time can provide an effective retraction speed (total retraction displacement over the total time of the pull-pause cycle) from about 10 microns per second to about 200 microns per second, from about 30 microns per second to about 120 microns per second, or from about 100 microns per second to about 140 microns per second.

[0103] In some cases, advancing the bonding stage away from the build surface includes advancing it away from the build surface in a vibrating manner. For example, advancing the bonding stage away from the build surface in a vibrating manner includes a cycle that includes (i) advancing the bonding stage away from the build surface and (ii) advancing the bonding stage back towards the build surface. Advancing the bonding stage away from the build surface in a vibrating manner can further include pausing the bonding stage between advancing the bonding stage away from the build surface and advancing the bonding stage back towards the build surface. Advancing the bonding stage away from the build surface in a vibrating manner can further include pausing the bonding stage after advancing the bonding stage back towards the build surface. An effective retreat speed (total retreat displacement performed over the total time of the vibration cycle) can be in the range of about 10 microns per second to about 200 microns per second, about 15 microns per second to about 120 microns per second, about 30 microns per second to about 120 microns per second, or about 100 microns per second to about 140 microns per second.

[0104] The layering / ridging effect is known to occur in known bottom-up printing systems as a result of the repelling phase moving upward and pinching off as the printed portion advances away. The upward movement and pinching off of the repelling phase are thought to be caused by a combination of the interfacial adhesion force between materials and the cavitation force formed when the printed portion moves away from the interface of the repelling phase and the polymerizable liquid. Although not intended to be restricted by theory, the layering effect is thought to be able to be mitigated by advancing the adhesion stage in a vibrating manner away from the build surface. For example, the adhesion stage is advanced 500 microns away from the build surface and then retracted 450 microns towards the build surface (thus having a net displacement of 50 microns away from the build surface). A large high-speed rise is thought to break the adhesion of the repelling phase from the solidified object, and thus the increased force results in a faster pinch, reducing surface ridging. In another example, the adhesion stage is rapidly advanced 500 microns away from the build surface, then rapidly retracted 520 microns towards the interface, and then slowly retracted 50 microns away from the build surface of the adhesion stage, resulting in a net movement of 30 microns per cycle and a net speed of 120 microns per second. By compressing the previous object layer against the newly polymerized object layer at the interface (i.e., the 520-micron reverse step following the 500-micron forward step), continuous cross-linking between layers can be achieved. To ensure continuous printing, the energy source can be projected continuously. Optionally, the energy source can intermittently pause polymerization while the object is not substantially adjacent to the interface.

[0105] Subsequently, advancing the stage away from the build surface can, in some cases, include a combination of continuous tension cycles and vibration cycles. Without intending to be bound by theory, continuous tension (having a constant or variable speed) can be used at the start of printing to reduce disruption of the printing interface that can occur from vibration cycles while the adhesion stage is immersed in the polymerizable liquid. Thus, after advancing the adhesion stage away from the build surface so that the adhesion stage is no longer immersed in the polymerizable liquid, a vibration cycle may be initiated.

[0106] In some embodiments, providing the polymerizable liquid step is performed by pressing the polymerizable liquid into the build region under pressure. In such cases, one or more advancing steps can be performed at a rate of at least 0.1, 1, 10, 50, 100, 500 or 1000 microns per second or more, either at an accumulated rate or an average rate. Generally, the pressure can be any amount sufficient to increase the rate of the advancing step by at least 2-fold, 4-fold, 6-fold, 8-fold or 10-fold compared to the maximum rate of repetition of the advancing step without applying the pressure. Pressure can be provided by housing the apparatus as described above in a pressure vessel and performing the process in a pressurized atmosphere (e.g., air, nitrogen-rich air, gas mixture, etc.), and pressures of 10, 20, 30 or 40 pounds per square inch (PSI) to 200, 300, 400 or 500 PSI or more can be used. For making large and irregular objects, higher pressures may not be preferred in view of the cost of large high-pressure vessels and slower fabrication times.

[0107] In contrast, when making smaller products, or when making rods or fibers that can be removed or withdrawn from a pressure vessel since the rods or fibers are manufactured through holes or openings in the pressure vessel, the size of the pressure vessel can be kept small compared to the size of the product being made and higher pressures can be more readily utilized (if desired).

[0108] In embodiments where the method includes a mobile phase, the mobile phase creates a shear force at the interface between the object to be printed and the mobile phase, which helps draw the polymerizable liquid into the build region, promotes replenishment of the depletion zone of the polymerizable liquid created when the solidified portion is extracted, and enables enhancing the resolution of the emerging object.

[0109] The methods disclosed herein can further include cooling at least one of the member, the repellent phase, the mobile phase, and the polymerizable liquid, or any combination thereof. Cooling of at least one of the member, the repellent phase, the mobile phase, and the polymerizable liquid can be achieved using the cooling devices described herein. In some embodiments, the cooling device can be configured to maintain the repellent phase in a non-liquid state. In some embodiments, the cooling device is optically transparent.

[0110] In some embodiments, the irradiating step is performed by patterned irradiation. The patterned irradiation can be a fixed pattern, depending on the specific product to be fabricated, or a variable pattern generated by a pattern generator (e.g., DLP, LCD, etc.) as discussed below.

[0111] When the patterned irradiation is a variable pattern rather than a pattern held constant over time, each irradiating step can be for any suitable time, or a duration depending on factors such as the intensity of the irradiation, the presence or absence of a dye in the polymerizable material, the growth rate, etc. Thus, in some embodiments, each irradiating step can be from 0.001, 0.01, 0.1, 1 or 10 microseconds to 1, 10 or 100 minutes or more in duration. In some embodiments, the interval between each irradiating step is preferably as short as possible, e.g., from 0.001, 0.01, 0.1 or 1 microsecond to 0.1, 1 or 10 seconds.

[0112] Exposing the build area to energy can include irradiating the build area with an energy source. Intended energy sources include electricity, chemistry, magnetism, electromagnetic, photons, acoustics, heating, and combinations thereof. Thus, one or more components of a suitable apparatus of the present disclosure, including but not limited to members, rejection phases, mobile phases, and / or cooling devices, can be optically transparent and / or can enable the conversion or transmission of energy provided by the energy source (e.g., electricity, chemistry, magnetism, electromagnetic, photons, acoustics, heating, and combinations thereof).

[0113] In some embodiments, the member and the rejection phase can be attached to an optical fiber projector that delivers energy for polymerization. In some embodiments, printing can occur in all directions.

[0114] The methods disclosed herein can further include filtering, washing, and / or contaminant removal of the mobile phase. The generation of small light-scattering particles of the polymerized ink can cause cloudiness of the mobile phase, which causes a loss of lateral resolution in printing and requires replacement of the interface after a certain number of prints. Filtering, washing, and / or contaminant removal of the mobile phase can remove small scattering particles, reduce cloudiness, and maintain appropriate lateral resolution over long or multiple prints.

[0115] By incorporating a cooling device that minimizes overheating at the interface that causes an exothermic polymerization reaction, cloudiness of the mobile phase can be further reduced. The cooling device can cool the mobile phase, and the cooling device can also cool the build area at the interface between the mobile phase and the polymerization liquid. In embodiments, the step of cooling the mobile phase includes passing the mobile phase through a cooling device. In embodiments, cooling the mobile phase is performed via a heat exchanger across the build area.

[0116] The method disclosed herein can further include oxygenating the mobile phase. Without intending to be bound by theory, it is believed that increasing the oxygen concentration in the mobile phase can further reduce the adhesion at the interface surface. In contrast to known methods that rely on the diffusion of oxygen through the membrane, oxygenating the mobile phase actively and advantageously transports the inhibitor in a controlled manner rather than relying on passive diffusion.

[0117] Device for forming a 3D object

[0118] Another aspect of the present disclosure provides an apparatus for forming a three-dimensional object from a polymerizable liquid, the apparatus comprising a support, an adhesion stage operably associated with the support on which the three-dimensional object is formed, a member having a rejection phase thereon, the rejection phase having a build surface, the rejection phase not being a liquid, the build surface and the adhesion stage defining a build region therebetween, a polymerizable liquid supply operably associated with the build for supplying the polymerizable liquid into the build region for solidification or polymerization, an energy source configured to deliver energy into the build region through the member to form a solid polymer from the polymerizable liquid, and at least one controller operably associated with the energy source for delivering energy into the build region, the at least one controller also being operably associated with the adhesion stage to advance the adhesion stage away from the build surface at a rate that depends on the energy intensity to form a three-dimensional object from the solid polymer.

[0119] In related aspects, the present disclosure provides an apparatus for forming a three-dimensional object from a polymerizable liquid, the apparatus comprising a support, an adhesion stage operably associated with the support on which the three-dimensional object is formed, a member having a repellent phase thereon, the repellent phase having a build surface, the build surface and the adhesion stage defining a build region therebetween, an optically transparent cooling device, a polymerizable liquid supply operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization, an energy source configured to deliver energy through the member to form a solid polymer from the polymerizable liquid, at least one controller operably associated with the energy source to deliver energy to the build region, the at least one controller also being operably associated with the cooling device to cool the build region, and the at least one controller also being operably associated with the adhesion stage to advance the adhesion stage away from the build surface at a rate that depends on the energy intensity to form a three-dimensional object from the solid polymer.

[0120] The methods of the present disclosure can be implemented with a variety of different apparatuses. In the simplest embodiment, an apparatus such as shown in FIG. 1 herein is used. In general, such an apparatus includes a container that includes an optically transparent member (window) for containing the reject phase, with a polymerizable liquid provided above the reject phase. The window is positioned at the bottom of the container, and energy may be delivered to the build region through the window to polymerize the polymerizable liquid. An adhesion stage is positioned above the container, and the growing three-dimensional object is gradually and progressively advanced upward out of the polymerizable liquid. At least one controller (e.g., a computer having a suitable interface and program) may be provided (not shown), and the at least one controller operates the adhesion stage and, optionally, a cooling device in response to data such as the current temperature of the reject phase determined, for example, by a temperature sensor. Additional and alternative features of the apparatus and its operation are discussed further below.

[0121] Many variations of the apparatus described in FIG. 1 above can be used. For example, the energy may be supplied through a window positioned at the bottom of the reject phase as shown in FIG. 1, through the side of the reject phase (aided, for example, by a mirror or mirror assembly within the reject phase), achieved using an energy source positioned within the fully polymerizable range, or achieved using an optical fiber or light pipe having a terminus within the polymerizable liquid. In an embodiment, the optically transparent member and the reject phase are attached to an optical fiber projector that delivers energy for polymerization.

[0122] The present disclosure provides an apparatus for forming a three-dimensional object from a polymerizable liquid, further comprising a support, an adhesion stage operably associated with the support, on which a three-dimensional object is formed, a member having a layer of a moving phase thereon, the moving phase having a build surface, the build surface and the adhesion stage defining a build region therebetween, a polymerizable liquid supply unit operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization, an energy source configured to deliver energy through the member into the build region to form a solid polymer from the polymerizable liquid, and at least one controller operably associated with the energy source for delivering energy into the build region, the at least one controller also being operably associated with the adhesion stage and configured to advance the adhesion stage away from the build surface at a rate depending on the energy intensity to form a three-dimensional object from the solid polymer.

[0123] The methods of the present disclosure can be implemented with a variety of different apparatuses. In the simplest embodiment, an apparatus such as that shown in FIG. 9 of this specification is used. Briefly, such an apparatus includes a container that includes an optically transparent member (window) for containing a moving phase, with a polymerizable liquid provided over a rejection phase. The window can be positioned at the bottom of the container, and energy can be delivered through the window into the build region to polymerize the polymerizable liquid. An adhesion stage can be positioned over the container, and a growing three-dimensional object can be advanced upwardly out of the polymerizable liquid gradually and incrementally from the polymerizable liquid. At least one controller (e.g., a computer with a suitable interface and program) for operating the adhesion stage can be provided (not shown). Additional and alternative features of the apparatus and its operation are discussed further below.

[0124] Many variations of the apparatus described in FIG. 9 above can be used. For example, energy can be supplied through a window positioned at the bottom of the mobile phase and through the side of the mobile phase (assisted, for example, by a mirror or mirror assembly in the mobile phase as shown in FIG. 14).

[0125] Generally, the members of the apparatus disclosed herein can be supports for the repellent phase and / or the mobile phase. Optionally, the members are optically transparent. Optionally, the members enable the conversion or transmission of energy provided by an energy source selected from the group consisting of electrical, chemical, magnetic, electromagnetic, photon, acoustic, heating, and combinations thereof. Optionally, the members are not oxygen permeable. As used herein, "not oxygen permeable" means that the member permeates less than 5%, less than 3%, or less than 1% by volume of the oxygen contained in the atmosphere to which the member is exposed. The members can be prepared from glass, low iron, and high transmission glass deformations, namely quartz, sapphire, soda lime (BK7) acrylic, fused silica, fused quartz, germanium, borosilicate, silicon nitride, or combinations thereof, as determined by the wavelength of the emitted energy source from the light engine.

[0126] As described above, the method of the present disclosure allows polymerization to occur without a strong adhesive force between the solidified polymer and the repellent phase thereunder, so the polymerizable liquid does not require a dead zone. Thus, in embodiments, the apparatus does not include a dead zone or an inhibition region. In embodiments, the optically transparent member is not oxygen permeable. Further, since the method of the present disclosure can use a non-liquid repellent phase and / or mobile phase, the build surface can be advantageously used in an all-directional manner and / or the interface can be formed in a curved shape such that it is molecularly smooth but not flat. Thus, in embodiments, the repellent phase is curved. In embodiments, the build surface is a horizontal plane. In embodiments, the build surface is a vertical plane.

[0127] In an embodiment, the apparatus includes a cooling device. Optionally, the cooling device is optically transparent. In an embodiment, the cooling device is operably associated with at least one of a member, a repellent phase, a mobile phase, and / or a polymerizable liquid. In an embodiment, the cooling device is a heat exchanger extending across the entire extent of the build region. In an embodiment, at least one controller is operably associated with the cooling device and is configured to maintain the repellent phase in a non-liquid state. In an embodiment, the cooling device is operably associated with at least one controller configured to control the temperature of at least one of a member, a mobile phase, and / or a polymerizable liquid.

[0128] The apparatus of the present disclosure can further include an outlet in fluid communication with the mobile phase and an inlet in fluid communication with the mobile phase. In an embodiment, the inlet is further in fluid communication with a first mobile phase supply reservoir and the outlet is further in fluid communication with a second mobile phase capture reservoir to enable flow of the mobile phase across the membrane. In an alternative embodiment, the outlet is in fluid communication with the inlet to provide a recirculation loop and enable flow of the mobile phase across the membrane.

[0129] The apparatus of the present disclosure can further include an outlet distribution nozzle in fluid communication with the mobile phase and including an outlet, and an inlet distribution nozzle in fluid communication with the mobile phase and including an inlet. The distribution nozzles advantageously facilitate the formation of a relatively uniform flow of the mobile phase across the build stage.

[0130] In embodiments where the outlet is in fluid communication with the inlet to provide a recirculation loop, the recirculation loop may further include a filtration unit provided along the recirculation loop between the outlet and the inlet, and the filtration unit may be operably associated with at least one controller configured to filter, clean, or remove contaminants from the mobile phase. The recirculation loop may further include a cooling device along the recirculation loop between the outlet and the inlet, and the cooling device may be operably associated with at least one controller configured to control the temperature of the mobile phase. The recirculation loop may further include an oxygenation unit along the recirculation loop between the outlet and the inlet, and the oxygenation unit may be operably associated with at least one controller configured to control the amount of oxygen provided to the mobile phase. In some embodiments, the recirculation loop includes a filtration unit, a cooling device, and an oxygenation unit. In some embodiments, the recirculation loop includes a filtration unit and a cooling device, a filtration unit and an oxygenation unit, or a cooling device and an oxygenation unit. In some embodiments, the recirculation loop includes a filtration unit. In some embodiments, the recirculation loop includes a cooling device. In some embodiments, the recirculation loop includes an oxygenation unit. In any embodiment where the recirculation loop includes a filtration unit, a cooling device, and an oxygenation unit, the filtration unit, the cooling device, and the oxygenation unit may be provided in any order along the circulation loop, for example, in the order of filtration unit, cooling device, oxygenation unit; filtration unit, oxygenation unit, cooling device; cooling device, filtration unit, oxygenation unit; cooling device, oxygenation unit, filtration unit; oxygenation unit, filtration unit, cooling device; or oxygenation unit, cooling device, filtration unit. In an embodiment, the recirculation loop is operably associated with at least one controller configured to maintain a continuous flow of the mobile phase. Optionally, the flow of the mobile phase is maintained at a constant rate.

[0131] In some embodiments, a simple gravity feed can be used, but a polymerizable liquid reservoir, piping, pump level sensors, and / or valves can be included to replenish a pool of polymerizable liquid (not shown). A drive device / actuator for the bonding stage can be included according to known techniques, along with associated wiring. In some embodiments, the drive / actuator, energy source, and in some embodiments, the pump and level sensors can all be operably associated with a suitable controller.

[0132] Depending on the particular polymerizable liquid being used, any suitable energy source (or combination of sources) can be used in the apparatus, including electron beam and ionizing radiation sources. In embodiments, the energy source is configured to provide energy to the build region through a member to form a solid polymer from the polymerizable liquid. In embodiments, the energy source is an optical engine. The optical engine transfers energy to initiate polymerization events in a patterned and / or controlled manner. Examples of optical patterning tools include digital micromirror devices or liquid crystal displays (LCDs). In embodiments, the optical engine has a light source selected from the group consisting of mercury light sources, light emitting diode (LED) light sources, halogen light, and lasers. In embodiments, the energy source is a thermal controller. In embodiments, the energy source is a microelectrode array. In embodiments, the energy source is a photoconductive material. In embodiments, the energy source is a magnetic flux. In embodiments, the energy source is selected from the group consisting of electrochemistry, electromagnetism, photoconductors, acoustics, heating, circuits, photodiodes, grid areas, and combinations thereof. In embodiments, the energy source is selected from the group consisting of electricity, chemistry, magnetism, electromagnetism, photons, acoustics, heating, and combinations thereof.

[0133] In an embodiment, the energy source is a radiation source, such as one or more light sources, particularly one or more ultraviolet light sources. Any suitable light source can be used, including incandescent bulbs, fluorescent lamps, phosphorescent or luminescent lamps, lasers, light emitting diodes, and arrays thereof. The light source preferably includes a patterning element operably associated with a controller. In an embodiment, the light source or patterning element includes a digital light processing (DLP), a spatial light modulator (SLM), or a digital (or deformable) micromirror device (DMD) having a microelectromechanical system (MEMS) mirror array, a mask (also known as a reticle), a silhouette, or a combination thereof. See U.S. Patent No. 7,902,526. Preferably, the light source includes a spatial light modulation array, such as a liquid crystal light valve array or a micromirror array, or a DMD (e.g., typically having a digital light processor operably associated therewith even under the control of a suitable controller), configured to expose or irradiate a polymerizable liquid without a mask, e.g., by maskless photolithography. See, e.g., U.S. Patent Nos. 6,312,134, 6,248,509, 6,238,852, and 5,691,541.

[0134] In some embodiments, the support on which the bonding stage is mounted can be an elevator that moves upward away from a stationary build surface, but in other embodiments, the reverse arrangement may be used. That is, the bonding stage can be on a fixed support, and the build surface can be lowered, thereby advancing the bonding stage away from the support. To achieve the same result, numerous different mechanical configurations will be apparent to those skilled in the art, and in all of them, the build surface is "stationary" in that no lateral (X or Y) movement is required or an elastic build surface that needs to be stretched and then rebounded (in connection with which the bonding stage is advanced and the bonding stage is retracted) is not required.

[0135] Depending on the choice of material from which the stage is fabricated and the choice of polymer liquid from which the article is made, the adhesion of the article to the adhesion stage may sometimes be insufficient to hold the article on the adhesion stage until the completion of the finished product or "build". For example, an aluminum adhesion stage may have lower adhesion than a poly(vinyl chloride) (or "PVC") adhesion stage. Thus, one solution is to use an adhesion stage containing PVC on the surface on which the article to be fabricated is polymerized. If this promotes adhesion too much such that the finished part cannot be conveniently separated from the adhesion stage, various techniques may optionally be used to further secure the article to a less adhesive adhesion stage, including but not limited to the application of an adhesive tape such as "Greener Masking Tape for Basic Painting #2025 High adhesion" to further secure the article to the adhesion stage during the fabrication process. Additionally, a polymer or metal mesh material can be secured to the stage such that the support formed early in the printing process polymerizes around the mesh and embeds a portion of the adhesion stage into the object itself.

[0136] In some embodiments of the soluble sacrificial layer, a soluble sacrificial layer or release layer can be placed between the adhesion stage and the three-dimensional object, such that the sacrificial layer can then be solubilized to conveniently release the three-dimensional object from the adhesion stage upon completion of fabrication. Any suitable sacrificial layer, such as an adhesive, can be used that can be coated on the adhesion stage or otherwise provided, and any suitable solvent (e.g., polar and non-polar organic solvents, aqueous solvents, etc.) can be used to solubilize the sacrificial release layer, provided that the sacrificial layer and its corresponding solvent are selected such that the specific material itself forming the three-dimensional object is not overly attacked or solubilized by the solvent. The sacrificial layer can be applied to the adhesion stage by any suitable technique, such as spraying, dip coating, painting, etc. Examples of materials suitable for the soluble sacrificial release layer (and non-limiting examples of corresponding solvents) include cyanoacrylate adhesives (acetone solvent), poly(vinylpyrrolidone) (water and / or isopropyl alcohol solvent), lacquers (acetone solvent), polyvinyl alcohol, polyacrylic acid, poly(methacrylic acid), polyacrylamide, polyalkylene oxides, such as poly(ethylene oxide), saccharides and carbohydrates, such as sucrose and dextran (all water or aqueous solvents), etc., but are not limited thereto. In some embodiments, solvents with lower surface energy are particularly preferred.

[0137] In some embodiments, the actuator / drive device and / or associated controller are configured only to advance the adhesion stage away from the build plate (e.g., in one direction). In some embodiments, the actuator / drive device and / or associated controller are configured as continuous drive (as opposed to step drive). The adhesion stage can be advanced away from the build stage at a constant or variable speed. In an embodiment, the adhesion stage can be advanced away from the build stage in a vibrating manner.

[0138] The controller for use in implementing the method of the present disclosure can be realized as a hardware circuit, software, or a combination thereof. In one embodiment, the controller is a general-purpose computer that executes software operably associated with a monitor, a drive device, a pump, and other components by appropriate interface hardware and / or software. Examples of software suitable for controlling the three-dimensional printing or fabrication methods and apparatuses described herein include, but are not limited to, the ReplicatorG open-source 3D printing program, the 3DPrint™ controller software of 3D Systems, Slic3r, Skeinforge, KISSlicer, Repetier-Host, PrintRun, Cura, and combinations thereof.

[0139] Process parameters for continuously or intermittently, directly or indirectly monitoring during the process (e.g., during one, several, or all of the filling, irradiating, and advancing steps) include, but are not limited to, energy intensity, temperature of the adhesion stage, polymerizable liquid in the build zone, temperature of the product being grown, temperature of the repelling phase, pressure, advancing speed, pressure, tension (e.g., exerted on the adhesion stage by the product being fabricated or grown), thickness of the release layer, and the like.

[0140] Known parameters that can be used in a feedback control system and / or a feedforward control system include, but are not limited to, the expected consumption of the polymerizable liquid (e.g., from the known shape or volume of the article to be fabricated), the decomposition temperature of the polymer formed from the polymerizable liquid, and the like.

[0141] (For example, during any or all of the steps of the process described above) As process conditions for continuously or stepwise, directly or indirectly controlling according to the parameters to be monitored and / or known parameters, the supply rate of the polymerizable liquid, temperature, pressure, the forward rate or forward speed of the adhesion stage, the intensity of the energy provided, the duration of the energy provided (e.g., for each "flakes"), etc. can be mentioned, but not limited to these.

[0142] For example, in order to determine whether the temperature exceeds the decomposition temperature of the polymerized product, the temperature of the polymerizable liquid or the temperature of the repelling phase in the build zone can be directly or indirectly monitored by an appropriate thermocouple, a non-contact temperature sensor (e.g., an infrared temperature sensor), or other appropriate temperature sensors. In that case, the process parameters can be adjusted by the controller to lower the temperature in the build zone and / or the temperature of the repelling phase. Examples of process parameters suitable for such adjustment may include lowering the temperature by a cooling device, lowering the forward rate of the adhesion stage, lowering the intensity of the energy provided, shortening the duration of the energy provided, etc.

[0143] In addition, the intensity of an energy source (e.g., an ultraviolet source such as a mercury lamp) can be monitored by a photodetector to detect a decrease in intensity from the irradiation source (e.g., due to the steady degradation of the irradiation source in use). If detected, the process parameters can be adjusted by the controller to adapt to the loss of intensity. Examples of process parameters suitable for such adjustment may include raising the temperature by a heater, lowering the forward rate of the adhesion stage, raising the power to the light source, etc.

[0144] As another example, control of temperature and / or pressure to extend the fabrication time can be achieved by heaters and coolers (individually or in combination with each other and in response to the controller separately), and / or by a pressure supply (e.g., pumps, pressure vessels, valves, and combinations thereof), and / or by a pressure relief mechanism such as a controllable valve (individually or in combination with each other and in response to the controller separately).

[0145] In embodiments where the energy source is light, the fabrication speed can be accelerated by increasing the light intensity. In some embodiments, the light is focused or "converged" on the build area to improve the fabrication speed. This can be achieved using an optical device such as an objective lens. The fabrication speed can generally be proportional to the intensity of the light. For example, the build speed (millimeters per hour) can be calculated by multiplying the light intensity (milliwatts per square centimeter) by a multiplier. The multiplier can depend on various factors including those described below. A series of multipliers can be used, ranging from low to high. In the lower range, the multiplier can be about 10, 15, 20, or 30. In the higher multiplier range, the multiplier can be about 150, 300, 400, or more.

[0146] To promote the fabrication speed, certain optical properties regarding the light can be selected. As an example, a band-pass filter can be used in combination with a mercury lamp light source to provide light with a wavelength of 365 ± 10 nm when measured at the full width at half maximum (FWHM). As a further example, a band-pass filter can be used in combination with an LED light source to provide light with a wavelength of 375 ± 15 nm when measured at the FWHM.

[0147] As described above, the polymerizable liquid used in such a process is a free-radical polymerizable liquid, or an acid-catalyzed or cationic polymerizable liquid. Some specific polymerizable liquids are, of course, more responsive to high speeds because they cure more rapidly or efficiently compared to others, which can be at least partially compensated for by a further increase in light intensity.

[0148] Generally, the lower the viscosity of the polymerizable liquid, the higher its adaptability to high speeds, especially when producing articles with a wide cross-sectional area and / or high density (however, this can be at least partially compensated by an increase in light intensity). The polymerizable liquid can have a viscosity in the range of 50 or 100 centipoise to 600, 800, or 1000 centipoise or more (measured at room temperature and atmospheric pressure using a suitable device such as a HYDRAMOTION REACTAVISC (trademark) Viscometer (manufactured by Hydramotion Ltd, York 25 Road Business Park, Malton, 1 York Y017 6YA England)). In some embodiments, the viscosity of the polymerizable liquid can be advantageously reduced by heating the polymerizable liquid as needed.

[0149] Manufactured article

[0150] The three-dimensional products manufactured by the methods and apparatuses of the present disclosure may be end products, finished products or substantially finished products, or intermediate products to be further processed in additional manufacturing processes such as surface treatment, laser cutting, electrical discharge machining, etc.

[0151] Using the methods and apparatuses of the present disclosure, a number of different products can be produced, including both large-scale models or prototypes, small quantities of custom products, small or ultra-small products or devices, etc. Examples include, but are not limited to, medical devices and implantable medical devices such as stents, drug delivery depots, functional structures, arrays of microneedles, fibers and rods such as waveguides, micro-mechanical elements, micro-fluidic elements, etc.

[0152] By the process described in this specification, products with various different properties can be manufactured. Thus, in some embodiments, the product is rigid, while in other embodiments, the product is flexible or elastic. In some embodiments, the product is solid, while in other embodiments, the product is a gel such as a hydrogel. In some embodiments, the product has shape memory (i.e., it substantially returns to its previous shape after deformation as long as the product does not deform to the structural break point). In some embodiments, the product is a single entity (i.e., formed from a single polymerizable liquid), while in some embodiments, the product is a composite (i.e., formed from two or more different polymerizable liquids). Specific properties will be determined by factors such as the choice of the polymerizable liquid used.

[0153] The methods and apparatuses according to the present disclosure can be better understood from the perspective of the following examples, which are merely intended to illustrate the structures and are by no means intended to limit these scopes.

Examples

[0154] Example 1: Organic-phase polymerizable liquid: Monomer / crosslinker with photoinitiator 1,6-Hexanediol diacrylate (HDDA) was used as the basis of the organic-phase polymerizable liquid. HDDA was procured from either Sigma-Aldrich or TCI America together with an inhibitor (100 ppm of monomethyl ether hydroquinone). These inhibitors were removed by base extraction before use. Briefly, 30 mL of 50 mM NaOH solution was added to 15 mL of the HDDA monomer solution and shaken. The inhibitor was deprotonated and extracted into the aqueous phase and removed with a separatory funnel. After shaking, salting out of the aqueous layer with NaCl (in the range of a final concentration of 1 - 2 M) was used to facilitate separation. Subsequently, extraction was performed twice with 50 mM NaOH 1 M NaCl solution and finally three times with 1 M NaCl solution. The monomer layer was recovered, dried over magnesium sulfate, and then isolated by vacuum filtration.

[0155] The pentaerythritol triacrylate and trimethylolpropane triacrylate (TMPTA) were subjected to the same post-treatment to remove the hydroquinone-based inhibitor.

[0156] The polymerizable liquid further contained a photoinitiator. 0.1 wt% to 0.5 wt% of each of 4,4'-bis(diethylamino)benzophenone (having a primary absorbance at about 370 nm), phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (having a primary absorbance at about 300 nm and a secondary absorbance at about 370 nm), and diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (having a primary absorbance at about 380 nm along with secondary absorbances at 370 nm and 390 nm) was individually added to the HDDA sample, and the HDDA sample was irradiated with a high-energy UV source (i.e., a high-pressure mercury lamp with emission in the region of 200 nm to 400 nm). All the initiators polymerized in the HDDA.

[0157] Therefore, Example 1 shows that the organic polymerizable liquid according to the present disclosure can be polymerized in the presence of an initiator by the energy source according to the present disclosure.

[0158] Example 2: Generation of 2D Images Printing experiments were carried out using high-density water (i.e., solutions saturated with dysprosium dioxide, saturated NaCl solution, and CsCl) and fluorinated solvents (perfluoro-n-hexane, perfluoro-n-octane) as repelling phases. 1 to 2 ml of the high-density repelling liquid was added to the bottom of the cuvette, and experiments were carried out using a fluorescent quartz cuvette (e.g., HDDA with 5% Irgacure 819) with the light monomer / initiator mixture of Example 1 added on top. A mask / pinhole was used to pattern the light from a collimated optical fiber connected to a high-pressure mercury lamp. The exposure ranged from 1 second to 30 seconds, and as a result, polymer droplets were formed at the interface.

[0159] Example 3: Printing of 3D Cylinders As in Example 2, a fluorescent quartz cuvette containing a repelling phase and a polymerizable liquid was prepared. On the other hand, a light extinction dye was added to the polymerizable liquid layer (i.e., an HDDA solution having 5% Irgacure 819 saturated with either naphthalene or anthracene) to limit the transmission of light into the polymerizable layer. By this addition, thin polymer disks about 200 μm thick were formed at the repelling interface. These thin polymer disks were crosslinked to the ends of the capillary tubes and formed a solidified layered structure when slowly retreating from the interface. The light source can be further modified by passing it through a 200-μm pinhole and then through a 15X UV-transmitting microscope objective lens with a working distance of 3 cm. After 30 seconds of irradiation, it was observed that polymer dots about 200 μm wide were floating at the interface. By focusing the lens at the end of the glass capillary tube and gradually retreating the capillary from the interface (about 100 μm / 30 s), a cylindrical pillar with a diameter of about 200 μm and a length of several millimeters can be formed.

[0160] Example 4: Perfluorinated repelling phase A fluorescence quartz cuvette containing a repellent phase and a polymerizable liquid was prepared as in Example 2, and a perfluorinated oil was used as the repellent phase. The perfluorinated oil contained Krytox GPL-100 and Krytox XHT-1000. Both could be laminated on the quartz window of the self-made fluid cell. On top of these fluorinated layers, a polymerizable fluid (HDDA, 5% by weight of Irgacure 819) was floated. The polymerizable liquid layer was irradiated through the quartz window supporting the liquid layer using one of a plurality of light sources (mercury lamp, UV-blue LED, halogen lamp). It was observed that a polymer pattern was formed at the fluorinated organic interface. These patterns could be controlled by the use of a masking layer, pinholes, or a digital micromirror device (DMD). After observing the 2D structures, again, these structures were formed by polymerization at the ends of capillary tubes or metal AFM chucks and then slowly retracted from the interface using a micropositioner. A series of masks (or DMD devices) could be used to project different patterns onto the interface to generate non-prismatic 3D structures.

[0161] Example 5: Gel-based repellent phase Hydrogels containing 2.5 wt% agar or agarose were formed by dissolving / mixing the solids of agar or agarose in DI water and swelling for 30 minutes. After this time, the mixture was heated in a microwave to its boiling point (loosely covering with a plastic cover to prevent evaporation of moisture from the mixture). The molten mixture was then poured into a Petri dish or a pattern (a glass window with a silicone spacer of about 1 mm at the edge) to form a thin agarose hydrogel window. These windows were cooled to a semi-solid state and rinsed / stored with DI water.

[0162] A quartz window with a 1-mm-thick agarose hydrogel on top was clamped to a custom-made fluid cell. A polymerizable liquid layer (95 wt% HDDA, 5 wt% Irgacure 819) was added to form a pool about 1 cm deep. As in Example 2, first, a 2D image was generated using patterned irradiation. Next, after attaching a 2D "base" on a stage (capillary tube, metal plate, etc.), the stage was retracted away from the interface at a speed in the range of 1 um / sec to 50 um / sec. As the retraction speed increased (and thus the polymerization speed also increased), permanent damage occurred on the hydrogel surface due to the excess heat generated from the polymerization reaction (i.e., water began to boil and the hydrogel surface deformed). These deformations did not limit the repelling properties of the surface (which generated a curved surface on the resulting object), but after the hydrogel penetrated and the hydrogel boiled, the contact between the quartz window and the polymerizable fluid was enabled and considered damaged.

[0163] Similar results were pre-generated by cross-linking of 2-(perfluorohexyl)ethyl acrylate monomer using 1 - 5 wt% 2-hydroxy-2-methylpropiophenone photoinitiator and then observed for a fluorogel swollen with perfluoropolymer Fluoriner FC-70.

[0164] Therefore, Example 5 demonstrates a method of forming a three-dimensional object according to the present disclosure using a repelling phase according to the present disclosure that is not a liquid.

[0165] Example 6: Use of a cooling stage The fluorinated oil / polymer liquid and gel / polymer liquid systems of Example 4 and Example 5 were used with a cooling device. A transparent cooling device was filled with acetone quenched with dry ice. The quenched acetone was passed between two optically transparent windows to continuously quench the recoiled phase. In the case of Krytox XHT-100, the coolant solidified the oil when the temperature dropped below the pour point of the oil (i.e., -5 °C). It was found important that the path between the patterned light source and the bottom of the quencher window was dry (i.e., a sealed plastic chamber containing a desiccant) to minimize ice formation and condensation on the window. Importantly, in all cases (gels and solidified oils), the cooling window enabled rapid and uniform heat dissipation during the polymerization process. Without such cooling, at higher build rates (i.e., rates exceeding 50 μm / sec), damage occurred to the smooth interface due to the exothermic polymerization reaction (as described in Example 4). When the cooling stage was used, multiple constructs were repeatedly and reliably produced at rates in the range of 150 μm / sec to 300 μm / sec. Constructs with a cross-sectional area of approximately 100 cm 2 and a height of 15 cm or more were achieved.

[0166] Accordingly, Example 6 demonstrates a method of forming a three-dimensional object according to the present disclosure using a recoiled phase according to the present disclosure in connection with an optically transparent cooling device across a build region rather than a liquid.

[0167] Example 7: Use of a Cooling Stage with a Multi-Projector System A custom water tank at the bottom of a 14-inch × 17-inch × 6-inch (width × length × height) low-iron glass was equipped with four 1-cm standoffs, such that the bottom surface of the water tank was lifted away from the surface on which it was placed. Thus, this water tank will have its bottom referred to as a "print bed" that constitutes a "member".

[0168] The bottom water tank of the second low-iron glass with larger dimensions was equipped with a distribution nozzle on one side and an overflow outlet on the other side, generating a uniform and unidirectional flow pattern between the inlet and the outlet. The inlet and outlet of this water tank were connected to a recirculating quench cooler and a filtration system, where the glycol aqueous solution was recirculated to keep the tank at a constant temperature in the range of -10°C to 25°C. Therefore, this system (water tank, nozzle, and recirculating quench cooler) is called the "cooling stage".

[0169] Two consumer-grade DLP projectors were modified to emit the maximum amount of UV light from their mercury lamps. This was achieved by removing the UV filter inside the projector housing, removing the "color wheel" responsible for generating red, green, and blue light, and changing the projection lens. Two of these projectors were mounted on an optical tracking system to enable alignment and tiling to generate an image projected over a 12-inch × 15-inch area at a projection distance of approximately 12 inches. Individually, each projector generated a 12-inch x 7.5-inch area. These projectors were connected to a custom computer system with software that could mirror the projected UV light image to a standard computer monitor and project an integrated image across the two tiled projectors. This system (aligned projectors modified to maximize UV, and the computer system) was the "light engine", "optical engine", or "optical engine". When not in use, the light projected from the light engine was removed by a shutter mechanism.

[0170] The light engine, cooling stage, and printing bed were vertically stacked within the support frame to create the configuration as depicted in Figure 4. Within the support frame, patterned UV light was projected upward from the light engine through the UV-transmissive cooling stage onto the UV-transmissive printing bed (low-iron glass that constitutes the "member"). Due to the 1 cm spacers that support the member, the glycol coolant could flow beneath the printing stage, actively cooling the reject phase and dissipating the heat generated immediately to the build area above the member.

[0171] A 4-foot linear actuator was mounted on top of the printing bed attached to the support frame. The actuator was mounted in a configuration substantially perpendicular to the plane generated by the member (the glass bottom surface of the printing bed). A support for holding an "adhesion stage" (a 12-inch by 12-inch perforated plate) whose plane was substantially parallel to the plane generated by the member was attached to the carriage of the actuator. The linear actuator was connected to the computer system that drives the light engine and programmed to move the adhesion stage 1 cm above the bottom of the printing bed (member) and then retract the adhesion stage in a systematical manner. The net retraction speed of the adhesion stage ranged from 10 micrometers per second to over 180 micrometers per second. This system was the "actuator" and the "adhesion stage". A schematic side view of the apparatus is shown in Figure 15.

[0172] Next, the stage was retracted from the printing bed, and a large amount of fluorinated oil (Krytox (trademark) oil from Chemours Company (Wilmington, DE) or Fomblin (registered trademark) oil from Solvay (Alpharetta, GA)) was poured onto the printing bed to create a repellent phase approximately 1 cm thick across the low-iron glass member. Then, the light engine was opened to generate a test image projected onto the air / fluorinated oil interface. The projected image was focused, and a fine alignment of the tile-type projector was performed to confirm that the image projected onto the interface was clear and continuous. Once completed, the light engine was closed, and the image sequence was loaded for the next printing. When the shutter was opened, the image sequence was projected.

[0173] After the fine alignment and closing of the light engine, the bonding stage was returned to the fluorinated oil repellent phase (the bottom of the vertical range of the actuator), and the vertical position of the stage was finely adjusted to just contact the liquid surface. Once in place, the polymerizable liquid was added to the printing bed to form a pool that floated on the underlying fluorinated oil repellent phase. After adding a sufficient supply of resin, the chiller stage was activated to bring the member and the repellent phase to an appropriate temperature (0 °C to 10 °C) and maintain that temperature.

[0174] The aforementioned polymerizable liquid and / or resin contained hexanediol diacrylate (HDDA) reactive monomer, acrylate-functionalized block copolymer, and 2% Irgacure 819 photoinitiator (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide). The mixture of copolymer resin, reactive diluent monomer, and photoinitiator was referred to as the "polymerizable liquid" or simply "resin".

[0175] The recoating resin was added to the printing bed. After the temperature of the recoiling phase stabilized, the shutter on the light engine was removed, allowing the patterned UV light to enter the printing bed. Next, the actuator (i.e., the adhesion stage) retracted away from the recoiling phase at a predetermined net speed. In the initial stage of polymerization, this speed was made slow to allow for stronger adhesion between the emerging printed objects with the adhesion stage itself. For example, when the object retracted away in a vibratory motion, the retraction speed was about 60 micrometers per second or less. When the object was retracted using continuous motion, the retraction speed was up to about 120 micrometers per second at most. Once the printing stage had completely emerged from the resin pool, the actuator retraction speed, and correspondingly the image projected by the light engine, increased to a speed exceeding 180 micrometers per second.

[0176] When a predetermined image sequence ended and the print was completed, the light engine was turned off. The actuator was commanded to lift the final object from the printing bed, and the residual resin dropped back onto the printing bed. The printed object still adhered to the adhesion stage was removed from the support actuator arm and washed in an organic solvent chemical bath to remove the unpolymerized liquid resin from the surface of the printed object. After thorough washing, the "green" object (i.e., not fully cured / hardened) was dried, carefully removed from the printing stage, then placed in a UV light oven to fully solidify its shape and achieve the intended material properties. After curing in the light oven, the finally solidified object was used and further tested.

[0177] This demonstrates that Example 7 forms a 3D object according to the present disclosure using a repelling liquid according to the present disclosure in combination with a transparent cooling device across a build area. Additionally, Example 7 demonstrates a faster printing speed (at least about 120 micrometers per second) across a large area (12 inches × 15 inches) that was not possible in the previous examples without using an optically transparent cooling device. Thus, Example 7 demonstrates the ability to array light engines, the alignment of said light engines, and the ability to print a single continuous object across multiple light engines.

[0178] Example 8: Use of a Mobile Phase with Cooling This system utilizes the same light engines, adhesion stage / actuator, and resin as described in Example 7. The two transparent beds that make up the cooling stage and the printing bed were replaced with a single transparent bed with distribution nozzles attached to both sides of the bed, as shown in FIG. 13. This unique transparent bed is the "printing bed", and the low-iron glass bottom thereof constitutes a member on which the repelling mobile phase can be disposed.

[0179] As in Example 7, an actuator arm that moves the light engines, the print bed, and the adhesion stage using a support frame was stacked vertically. As described above, the light engines projected patterned light upward through the transparent bottom (member) of the printing bed and the fluorinated oil (repelling phase) to initiate solidification of the resin (polymerizable fluid). There is no secondary transparent bed that constitutes the optically transparent cooler used in this example, although this is optionally possible.

[0180] Two dispensing nozzles on both sides of the printing bed were used as inlets and outlets, with fluorinated oil acting as the mobile phase and recirculated through the bed in a relatively uniform flow field across the build area. The 12-inch x 15-inch projection area generated by the light engine was placed between the two dispensing nozzles. When the fluorinated oil is pumped out of the printing bed, it is optionally filtered, quenched, and oxygenated. In this example, the oil is passed through a filtration system to remove microparticles that could cause unwanted light scattering, and the quencher only directly cools the oil. Oxygenation of the reject phase is not necessary but is optional and can improve the possible final printing speed.

[0181] When the fluorinated oil was placed in the printing bed so as to completely immerse it in the nozzles and at the nozzle outlets, it was recirculated and the adhesion stage was retracted from the air-oil interface. At this point, the light engine was opened to generate a test image projected onto the air / fluorinated-oil interface. The projection image was focused and the fine alignment of the tile-type projector was carried out, and it was confirmed that the image projected onto the interface was clear and continuous. When completed, the light engine was closed and the image sequence was loaded for the next printing. When the shutter was opened, the image sequence was projected.

[0182] After the precise alignment and closing of the light engine, the adhesion stage was returned to the fluorinated oil reject phase (the bottom of the vertical range of the actuator), and the vertical position of the stage was finely adjusted to just touch the liquid surface. The adhesion stage was positioned in place, and the recirculation of the mobile phase was temporarily stopped while the resin was added to the printing bed, forming a resin pool floating in the underlying fluorinated oil reject phase. After the resin was sufficiently added and supplied, the recirculation of the mobile phase was restarted. Due to the position of the dispensing nozzles below the fluorinated oil / resin interface, only oil was drawn out through the recirculation loop. Once the oil recirculation continued, the quenching device placed within the recirculation loop was activated until the mobile phase reached an appropriate temperature of about 0°C to 10°C.

[0183] The coincidence resin was added to the printing bed. After the temperature of the mobile phase stabilized, the shutter on the light engine was removed, allowing the patterned UV light to enter the printing bed. Next, the actuator (i.e., the adhesion stage) retracted away from the recoating phase at a predetermined net speed. In the initial stage of polymerization, this speed was made slow to enable stronger adhesion between the emerging printed objects involving the adhesion stage itself. Once the printing stage completely emerged from the resin pool, the actuator retraction speed, and correspondingly the image projected by the light engine, increased to a speed exceeding 180 micrometers per second.

[0184] The movement of the recoating phase relative to the emerging printed objects generated shear forces that reduced the adhesion interaction between these emerging printed objects and the recoating phase. As a result, the emerging printed objects were found to have excellent lateral (X - Y) resolution and surface finish compared to printing from the same phase when held stationary and cooled as disclosed in Example 7.

[0185] When a predetermined image sequence ended and the printed object was completed, the light engine was turned off. The actuator was commanded to lift the final object from the printing bed, and the residual resin dropped back onto the printing bed. The cooling and recirculation of the mobile phase were stopped. The printed object still adhered to the printing stage was removed from the support actuator arm and washed in an organic solvent chemical bath to remove the unpolymerized liquid resin from the surface of the printed object. After thorough washing, the "green" object (i.e., not fully cured / set) was dried, carefully removed from the printing stage, and then placed in a UV light oven to fully solidify its shape and fully react to achieve the intended material properties. After curing in the light oven, the finally solidified object was used and further tested.

[0186] In contrast to Example 7, where a glycol solution was used as an intermediate in a transparent heat exchanger, the ejection phase was directly and actively cooled, increasing the heat removal rate during printing and providing good thermal stability. Additionally, as described above, in known systems, for longer prints, there is typically an accumulation of small particulate polymers that induce unwanted light scattering in the build region, thereby causing a loss of lateral resolution. This phenomenon in the field of SLA 3D printing is often referred to as "clouding", and the only solution is to replace the ejection phase. In this scenario, after printing is complete, the ejection phase needs to be removed and vacuum filtered to remove such particles. Therefore, due to continuous filtration and regeneration during printing, there is a significant advantage over other techniques in that the ejection interface can be recycled. This is advantageous because the printer can continue printing for a longer period and produce a greater quantity before maintenance is required.

[0187] Accordingly, Example 8 demonstrates a method of forming a three-dimensional object using a mobile phase that is cooled. Thus, Example 8 demonstrates a method for continuously regenerating the build interface by removing particulate contaminants formed during the printing process from the ejection phase and the mobile phase, and an increased printing resolution resulting from the low adhesion between the mobile phase and the emerging object.

[0188] The following embodiments are also disclosed in the present disclosure. [Embodiment 1] A method of forming a three-dimensional object, comprising: providing an adhesion stage and a member, the member having an ejection phase thereon, the ejection phase having a build surface, the adhesion stage and the build surface defining a build region therebetween; providing a polymerizable liquid to the build region, the polymerizable liquid being immiscible with the ejection phase; By exposing the build region to energy through at least a part of the ejection phase, polymerizing the polymerizable liquid to form a solid polymer from the polymerizable liquid, and advancing the adhesion stage away from the build surface to form the three-dimensional object made of the solid polymer. The method wherein the ejection phase is not a liquid. [Embodiment 2] The method according to Embodiment 1, further comprising cooling at least one of the member, the ejection phase, or the polymerizable liquid. [Embodiment 3] A method for forming a three-dimensional object, Providing an adhesion stage, a member, and a cooling device, wherein the member has an ejection phase thereon, the member is between the cooling device and the ejection phase, the ejection phase has a build surface, and the adhesion stage and the build surface define a build region therebetween. Providing a polymerizable liquid to the build region, wherein the polymerizable liquid is immiscible with the ejection phase. By exposing the build region to energy through at least a part of the cooling device and at least a part of the ejection phase, polymerizing the polymerizable liquid to form a solid polymer from the polymerizable liquid, and advancing the adhesion stage away from the build surface to form the three-dimensional object made of the solid polymer. [Embodiment 4] The method according to Embodiment 2 or 3, wherein the cooling device is optically transparent. [Embodiment 5] The method according to any one of Embodiments 1 to 4, wherein the member is optically transparent. [Embodiment 6] The method according to any one of Embodiments 1 to 4, wherein the member enables conversion or transmission of energy provided by an energy source selected from the group consisting of electricity, chemistry, magnetism, electromagnetism, photons, acoustics, heating, and combinations thereof. [Embodiment 7] The method according to any one of Embodiments 1 to 6, wherein the repellent phase and the polymerizable liquid have a contact angle greater than 60°. [Embodiment 8] The method according to Embodiment 7, wherein the repellent phase and the polymerizable liquid have a contact angle greater than 60° when the polymerizable liquid substantially does not contain a surfactant. [Embodiment 9] The method according to any one of Embodiments 1 to 7, wherein the polymer liquid further contains a surfactant. [Embodiment 10] The method according to any one of Embodiments 1 to 9, wherein the polymerizable liquid does not contain a dead zone. [Embodiment 11] The method according to any one of Embodiments 1 to 10, wherein the polymer liquid contains an aqueous polymer liquid. [Embodiment 12] The method according to Embodiment 11, wherein the polymer liquid contains a monomer or oligomer selected from the group consisting of acrylic, methacrylic, urethane, acrylic ester, polyester, cyano ester, acrylamide, maleic anhydride, functionalized PEGs, dimethacrylate oligomer, and combinations thereof. [Embodiment 13] The method according to any one of Embodiments 1 to 10, wherein the polymer liquid contains an organic polymer liquid. [Embodiment 14] The method according to Embodiment 13, wherein the polymer liquid contains a monomer or oligomer selected from the group consisting of olefin, halogenated olefin, cyclic alkene, alkene, alkyne, and combinations thereof. [Embodiment 15] The method according to any one of Embodiments 1 to 14, wherein the repellent phase contains a gel. [Embodiment 16] The method according to Embodiment 15, wherein the gel is selected from the group consisting of organic gel, silicone gel, aqueous hydrogel, fluorogel, and combinations thereof. [Embodiment 17] The gel is an aqueous hydrogel, and the aqueous hydrogel is selected from the group consisting of agar, agarose gel, polyacrylamide gel, starch gel, cation gel, anion gel, and combinations thereof, according to the method of Embodiment 16. [Embodiment 18] The gel is a fluorogel, and the fluorogel contains 2-(perfluorohexyl)ethyl acrylate swollen with perfluoropolyether, according to the method of Embodiment 17. [Embodiment 19] The ejection phase contains a solid, according to the method of any one of Embodiments 1 to 14. [Embodiment 20] The solid is selected from the group consisting of organic solids, aqueous solids, perfluorinated solids, and combinations thereof, according to the method of Embodiment 19. [Embodiment 21] The solid is an organic solid, and the organic solid is selected from the group consisting of squalane, squalene, solid hexadecane, and combinations thereof, according to the method of Embodiment 20. [Embodiment 22] The solid is an aqueous solid, and the aqueous solid is selected from the group consisting of ice, solid tetraethylene glycol, solid PEG-300, solid PEG-400, solid PEG-600, and combinations thereof, according to the method of Embodiment 20. [Embodiment 23] The solid is a perfluorinated solid, and the perfluorinated solid contains solid perfluoropolyether, fluorinated ethylene propylene, or polytetrafluoroethylene, according to the method of Embodiment 20. [Embodiment 24] The ejection phase contains a gas, according to the method of any one of Embodiments 1 to 14. [Embodiment 25] The ejection phase contains a liquid, according to the method of any one of Embodiments 3 to 14. [Embodiment 26] The liquid is an aqueous liquid, an organic liquid, a silicone liquid, or a fluorine liquid, according to the method of Embodiment 25. [Embodiment 27] The method according to embodiment 26, wherein the aqueous liquid contains water, deuterium oxide, a concentrated salt solution, or a concentrated sugar solution. [Embodiment 28] The method according to embodiment 26, wherein the organic liquid contains an organic oil. [Embodiment 29] The method according to embodiment 26, wherein the silicone liquid contains a silicone oil. [Embodiment 30] The method according to embodiment 26, wherein the fluorine liquid contains a fluorinated oil. [Embodiment 31] The method according to any one of embodiments 1 to 30, wherein the polymerization liquid contains granular or colloidal substances that can bond together. [Embodiment 32] The method according to any one of embodiments 1 to 31, wherein the polymerization liquid contains metal ions that can deposit to form a bulk metal. [Embodiment 33] The method according to any one of embodiments 1 to 32, wherein the ejection phase is optically transparent. [Embodiment 34] The method according to any one of embodiments 1 to 33, wherein the ejection phase is curved. [Embodiment 35] The method according to any one of embodiments 1 to 34, wherein the member is not oxygen permeable. [Embodiment 36] The method according to any one of embodiments 1 to 35, wherein the polymerization is carried out by electromagnetic irradiation. [Embodiment 37] The method according to any one of embodiments 1 to 36, wherein the polymerization is carried out by electricity. [Embodiment 38] The method according to any one of embodiments 1 to 37, wherein the polymerization is carried out by thermal activation. [Embodiment 39] The method according to any one of embodiments 1 to 38, wherein the polymerization is carried out by magnetic activation. [Embodiment 40] The method according to any one of Embodiments 1 to 39, wherein the method is performed in parallel using a multi-chip array, and the chips of the multi-chip array include the member. [Embodiment 41] The method according to Embodiment 40, wherein the multi-chip array is part of a beam pen lithography system. [Embodiment 42] The method according to Embodiment 40, wherein the multi-chip array is part of a polymer pen lithography system. [Embodiment 43] The method according to any one of Embodiments 1 to 39, wherein the member and the ejection phase are attached to an optical fiber projector, and the optical fiber projector delivers energy for polymerization. [Embodiment 44] The method according to any one of Embodiments 1 to 43, wherein the printing occurs omnidirectionally. [Embodiment 45] The method according to any one of Embodiments 1 to 44, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a constant speed. [Embodiment 46] The method according to any one of Embodiments 1 to 44, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a variable speed. [Embodiment 47] The method according to any one of Embodiments 1 to 44, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a constant speed for a fixed distance, then pausing for a fixed time, and optionally repeating. [Embodiment 48] Advancing the adhesion stage away from the build surface includes advancing the adhesion stage a fixed distance at a variable speed away from the build surface, then pausing for a fixed time, and optionally repeating, according to any one of embodiments 1 to 44. [Embodiment 49] Advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface in an oscillating manner, according to any one of embodiments 1 to 44. [Embodiment 50] Advancing the adhesion stage away from the build surface in an oscillating manner includes a cycle of (i) advancing the adhesion stage away from the build surface and (ii) advancing the adhesion stage back towards the build surface, according to embodiment 49. [Embodiment 51] The method according to embodiment 50 further includes pausing the adhesion stage between advancing the adhesion stage away from the build surface and advancing the adhesion stage back towards the build surface. [Embodiment 52] The method according to embodiment 50 or 51 further includes pausing the adhesion stage once after advancing the adhesion stage back towards the build surface. [Embodiment 53] An apparatus for forming a three-dimensional object from a polymerizable liquid, a support, an adhesion stage operably associated with the support, on which the three-dimensional object is formed, a member having a repellent phase layer thereon, the repellent phase having a build surface, the repellent phase not being a liquid, and the build surface and the adhesion stage defining a build region therebetween, A polymerizable liquid supply unit that is operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization; An energy source configured to deliver energy through the member to form a solid polymer from the polymerizable liquid in the build region; At least one controller operably associated with the energy source for delivering energy to the build region, wherein the at least one controller is also operably associated with the adhesion stage to advance the adhesion stage away from the build surface at a speed that depends on the energy intensity to form the three-dimensional object from the solid polymer, and at least one controller. An apparatus comprising: [Embodiment 54] The apparatus according to embodiment 53, further comprising an optically transparent cooling device. [Embodiment 55] An apparatus for forming a three-dimensional object from a polymerizable liquid, A support; An adhesion stage operably associated with the support, on which the three-dimensional object is formed; A member having a repellent phase layer thereon, the repellent phase having a build surface, and the build surface and the adhesion stage defining a build region therebetween; An optically transparent cooling device; A polymerizable liquid supply unit that is operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization; An energy source configured to deliver energy through the member to form a solid polymer from the polymerizable liquid in the build region; At least one controller operably associated with the energy source to deliver energy to the build area, wherein the at least one controller is also operably associated with the cooling device to cool the build area, and the at least one controller is also operably associated with the adhesion stage to advance the adhesion stage away from the build surface at a speed that depends on the energy intensity to form a three-dimensional object from the solid polymer. An apparatus comprising: at least one controller. [Embodiment 56] The apparatus according to any one of Embodiments 53 to 55, wherein the member is optically transparent. [Embodiment 57] The apparatus according to any one of Embodiments 53 to 55, wherein the member enables conversion or transmission of energy provided by an energy source selected from the group consisting of electricity, chemistry, magnetism, electromagnetism, photons, acoustics, heating, and combinations thereof. [Embodiment 58] The apparatus according to any one of Embodiments 53 to 57, wherein the apparatus does not include a dead zone. [Embodiment 59] The apparatus according to any one of Embodiments 54 to 58, wherein the optically transparent cooling device is operably associated with at least one of the member, the rejection phase, and the polymerizable liquid. [Embodiment 60] The apparatus according to any one of Embodiments 54 to 59, wherein the optically transparent cooling device is a heat exchanger that extends over the entire range of the build area. [Embodiment 61] The apparatus according to any one of Embodiments 54 to 60, wherein the at least one controller is operably associated with the optically transparent cooling device and is configured to maintain the rejection phase in a non-liquid state. [Embodiment 62] The apparatus according to any one of Embodiments 54 to 61, wherein the rejection phase is curved. [Embodiment 63] The apparatus according to any one of Embodiments 53 to 62, configured to provide an energy source to the build area through the member to form a solid polymer from the polymerizable liquid. [Embodiment 64] The apparatus according to any one of Embodiments 53 to 63, wherein the bonding stage is operably associated with an operating arm configured to advance the bonding stage away from the build stage. [Embodiment 65] The apparatus according to any one of Embodiments 53 to 64, wherein the energy source is an optical engine. [Embodiment 66] The apparatus according to Embodiment 65, wherein the optical engine has a light source selected from the group consisting of a mercury light source, an LED light source, halogen light, and a laser. [Embodiment 67] The apparatus according to any one of Embodiments 53 to 64, wherein the energy source is a thermal controller. [Embodiment 68] The apparatus according to any one of Embodiments 53 to 64, wherein the energy source is selected from the group consisting of electricity, chemistry, magnetism, electromagnetic, photon, acoustic, heating, and combinations thereof. [Embodiment 69] The apparatus according to any one of Embodiments 53 to 68, wherein the member is not oxygen permeable. [Embodiment 70] The apparatus according to any one of Embodiments 53 to 69, wherein the build surface is a horizontal plane. [Embodiment 71] The apparatus according to any one of Embodiments 53 to 69, wherein the build surface is a vertical plane. [Embodiment 72] The apparatus according to any one of Embodiments 53 to 69, wherein the build surface is omnidirectional. [Embodiment 73] A method of forming a three-dimensional object, comprising: To provide a build stage and a member, wherein the member has a mobile phase thereon, the mobile phase has a build surface, and the build stage and the build surface define a build region therebetween; To provide a polymerizable liquid to the build region, wherein the polymerizable liquid is immiscible with the mobile phase; To polymerize the polymerizable liquid by exposing the build region to energy through at least a portion of the mobile phase to form a solid polymer from the polymerizable liquid, and to advance the build stage away from the build surface to form the three-dimensional object comprising the solid polymer. A method comprising the above steps. [Embodiment 74] The method according to embodiment 73, wherein the mobile phase comprises a moving solid phase, a moving gel phase, a flowing fluid, or a combination thereof. [Embodiment 75] The method according to embodiment 74, wherein the moving solid phase is selected from the group consisting of organic solids, aqueous solids, perfluorinated solids, and combinations thereof. [Embodiment 76] The method according to embodiment 75, wherein the organic solid is selected from the group consisting of squalane, squalene, solid hexadecane, and combinations thereof. [Embodiment 77] The method according to embodiment 75, wherein the aqueous solid is selected from the group consisting of ice, solid tetraethylene glycol, solid PEG-300, solid PEG-400, solid PEG-600, and combinations thereof. [Embodiment 78] The method according to embodiment 75, wherein the perfluorinated solid is selected from the group consisting of perfluoropolyethers, fluorinated ethylene propylene, polytetrafluoroethylene, and combinations thereof. [Embodiment 79] The method according to embodiment 74, wherein the moving gel phase is selected from the group consisting of organic gels, silicone gels, aqueous hydrogels, fluorogels, and combinations thereof. [Embodiment 80] The method according to embodiment 79, wherein the aqueous hydrogel is selected from the group consisting of agar, agarose gel, polyacrylamide gel, starch gel, cation gel, anion gel, and combinations thereof. [Embodiment 81] The method according to embodiment 79, wherein the fluorogel contains 2-(perfluorohexyl)ethyl acrylate swollen with perfluoropolyether. [Embodiment 82] The method according to embodiment 74, wherein the flowing fluid is selected from the group consisting of an aqueous liquid, an organic liquid, a silicone liquid, and a fluorine liquid. [Embodiment 83] The method according to embodiment 82, wherein the flowing fluid contains an aqueous liquid selected from the group consisting of water, deuterium oxide, a concentrated salt solution, and a concentrated sugar solution. [Embodiment 84] The method according to embodiment 82, wherein the flowing fluid contains a silicone liquid containing silicone oil. [Embodiment 85] The method according to embodiment 82, wherein the flowing fluid contains a fluorine liquid containing a fluorinated oil. [Embodiment 86] The method according to embodiment 82, wherein the flowing fluid contains an organic liquid containing an organic oil. [Embodiment 87] The method according to any one of embodiments 73 to 86, wherein the mobile phase includes a rejection phase. [Embodiment 88] The method according to any one of embodiments 73 to 87, wherein the mobile phase is recycled through a closed loop. [Embodiment 89] The method according to any one of embodiments 73 to 88, further including one or more of filtration, washing, and contamination removal of the mobile phase. [Embodiment 90] The method according to any one of embodiments 73 or 89, further including cooling the mobile phase. [Embodiment 91] The method according to embodiment 90, wherein cooling the mobile phase includes passing the mobile phase through a cooling device. [Embodiment 92] The method according to embodiment 90, wherein cooling the mobile phase is performed via a heat exchanger across the build region. [Embodiment 93] The method according to any one of embodiments 73 to 92, further comprising oxygenating the mobile phase. [Embodiment 94] The method according to any one of embodiments 73 to 93, wherein the member is optically transparent. [Embodiment 95] The method according to any one of embodiments 73 to 94, wherein the member enables conversion or transmission of energy provided by an energy source selected from the group consisting of electricity, chemistry, magnetism, electromagnetism, photons, acoustics, heating, and combinations thereof. [Embodiment 96] The method according to any one of embodiments 73 to 95, wherein the mobile phase and the polymerizable liquid have a contact angle greater than 60°. [Embodiment 97] The method according to any one of embodiments 73 to 96, wherein the polymer liquid does not include a dead zone. [Embodiment 98] The method according to any one of embodiments 73 to 97, wherein the polymer liquid is an aqueous polymer liquid. [Embodiment 99] The method according to embodiment 98, wherein the polymer liquid includes a monomer or oligomer selected from the group consisting of acrylic, methacrylic, urethane, acrylate, polyester, cyanoester, acrylamide, maleic anhydride, functionalized PEGs, dimethacrylate oligomers, and combinations thereof. [Embodiment 100] The method according to any one of embodiments 73 to 99, wherein the polymer liquid is an organic polymer liquid. [Embodiment 101] The method according to embodiment 100, wherein the polymerization liquid comprises a monomer or oligomer selected from the group consisting of olefins, halogenated olefins, cyclic alkenes, alkenes, alkynes, and combinations thereof. [Embodiment 102] The method according to any one of embodiments 73 to 101, wherein the polymerization liquid comprises a granular or colloidal substance that can be covalently bonded. [Embodiment 103] The method according to any one of embodiments 73 to 101, wherein the polymerization liquid comprises metal ions that can deposit to form bulk metal. [Embodiment 104] The method according to any one of embodiments 73 to 103, wherein the mobile phase is optically transparent. [Embodiment 105] The method according to any one of embodiments 73 to 104, wherein at least one of the polymerizable liquid and the mobile phase further comprises a surfactant. [Embodiment 106] The method according to any one of embodiments 73 to 105, wherein both the polymerizable liquid and the mobile phase further comprise a surfactant. [Embodiment 107] The method according to any one of embodiments 73 to 106, wherein the member is not oxygen permeable. [Embodiment 108] The method according to any one of embodiments 73 to 107, wherein the polymerization is carried out by at least one of irradiation, electrical activation, thermal activation, and magnetic activation. [Embodiment 109] The method according to any one of embodiments 73 to 108, wherein the method is carried out in parallel using a multi-chip array, and the chips of the multi-chip array comprise the member. [Embodiment 110] The method according to embodiment 109, wherein the multi-chip array is part of a beam pen lithography system. [Embodiment 111] The method according to Embodiment 109, wherein the multi-chip array is part of a polymer pen lithography system. [Embodiment 112] The method according to any one of Embodiments 73 to 111, wherein the printing occurs omnidirectionally. [Embodiment 113] The method according to any one of Embodiments 73 to 112, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a constant speed. [Embodiment 114] The method according to any one of Embodiments 73 to 112, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a variable speed. [Embodiment 115] The method according to any one of Embodiments 73 to 112, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a constant speed for a fixed distance, then pausing for a fixed time, and optionally repeating. [Embodiment 116] The method according to any one of Embodiments 73 to 112, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a variable speed for a fixed distance, then pausing for a fixed time, and optionally repeating. [Embodiment 117] The method according to any one of Embodiments 73 to 112, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface in a vibrating manner. [Embodiment 118] The method according to Embodiment 117, wherein advancing the bonding stage away from the build surface in a vibrating manner includes a cycle that includes (i) advancing the bonding stage away from the build surface and (ii) advancing the bonding stage back toward the build surface. [Embodiment 119] The method according to Embodiment 118, further including temporarily stopping the bonding stage between advancing the bonding stage away from the build surface and advancing the bonding stage back toward the build surface. [Embodiment 120] The method according to Embodiment 117 or Embodiment 118, further including temporarily stopping the bonding stage after advancing the bonding stage back toward the build surface. [Embodiment 121] An apparatus for forming a three-dimensional object from a polymerizable liquid, comprising: a support; a bonding stage operably associated with the support, on which the three-dimensional object is formed; a member having a layer of a mobile phase thereon, the mobile phase having a build surface, the build surface and the bonding stage defining a build region therebetween; a polymerizable liquid supply operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization; an energy source configured to deliver energy through the member to form a solid polymer from the polymerizable liquid in the build region; At least one controller operably associated with the energy source to deliver energy to the build area, wherein the at least one controller is also operably associated with the adhesion stage to move the adhesion stage away from the build surface at a speed that depends on the energy intensity to form the three-dimensional object from the solid polymer, and at least one controller. [Embodiment 122] The apparatus according to embodiment 121, further comprising a cooling device operably associated with at least one of the member, the mobile phase, and the polymerizable liquid. [Embodiment 123] The apparatus according to embodiment 122, wherein the cooling device is optically transparent. [Embodiment 124] The apparatus according to embodiment 122 or 123, wherein the cooling device is a heat exchanger across the build area. [Embodiment 125] The apparatus according to any one of embodiments 122 to 124, wherein the cooling device is operably associated with at least one controller configured to control the temperature of at least one of the member, the mobile phase, and the polymerizable liquid. [Embodiment 126] The apparatus according to any one of embodiments 121 to 125, wherein the adhesion stage is operably associated with an actuating arm configured to advance the adhesion stage. [Embodiment 127] The apparatus according to any one of embodiments 121 to 126, wherein the mobile phase includes a moving solid phase, a moving gel phase, a flowing fluid, or a combination of the foregoing. [Embodiment 128] The apparatus according to embodiment 127, wherein the moving solid phase is selected from the group consisting of organic solids, aqueous solids, perfluorinated solids, and combinations thereof. [Embodiment 129] The device according to embodiment 128, wherein the organic solid is selected from the group consisting of squalane, squalene, solid hexadecane, and combinations thereof. [Embodiment 130] The device according to embodiment 128, wherein the aqueous solid is selected from the group consisting of ice, solid tetraethylene glycol, solid PEG-300, solid PEG-400, solid PEG-600, and combinations thereof. [Embodiment 131] The device according to embodiment 128, wherein the perfluorinated solid is selected from the group consisting of perfluoropolyether, fluorinated ethylene propylene, polytetrafluoroethylene, and combinations thereof. [Embodiment 132] The device according to embodiment 127, wherein the moving gel phase is selected from the group consisting of organic gels, silicone gels, aqueous hydrogels, fluorogels, and combinations thereof. [Embodiment 133] The device according to embodiment 132, wherein the aqueous hydrogel is selected from the group consisting of agar, agarose gel, polyacrylamide gel, starch gel, cationic gel, anionic gel, and combinations thereof. [Embodiment 134] The device according to embodiment 132, wherein the fluorogel contains 2-(perfluorohexyl)ethyl acrylate swollen with perfluoropolyether. [Embodiment 135] The device according to embodiment 127, wherein the flowing fluid is selected from the group consisting of aqueous liquids, organic liquids, silicone liquids, and fluorine liquids. [Embodiment 136] The device according to embodiment 135, wherein the aqueous liquid is selected from the group consisting of water, deuterium oxide, concentrated salt solution, and concentrated sugar solution. [Embodiment 137] The device according to embodiment 135, wherein the silicone liquid contains silicone oil. [Embodiment 138] The apparatus according to embodiment 135, wherein the fluorine liquid contains a fluorinated oil. [Embodiment 139] The apparatus according to embodiment 135, wherein the organic liquid contains an organic oil. [Embodiment 140] The apparatus according to any one of embodiments 121 to 139, wherein the mobile phase contains a repellent phase. [Embodiment 141] The apparatus according to any one of embodiments 121 to 140, further comprising an outlet in fluid communication with the mobile phase and an inlet in fluid communication with the mobile phase. [Embodiment 142] The apparatus according to embodiment 141, wherein the outlet is in fluid communication with the inlet to provide a recirculation loop and enable the flow of the mobile phase across the membrane. [Embodiment 143] The apparatus according to embodiment 141 or 142, further comprising an outlet distribution nozzle in fluid communication with the mobile phase and including the outlet, and an inlet distribution nozzle in fluid communication with the mobile phase and including the inlet. [Embodiment 144] The apparatus according to embodiment 142 or 143, further comprising a filtration unit provided along the recirculation loop between the outlet and the inlet, the filtration unit being operably associated with at least one controller configured to filter, clean, or remove contaminants from the mobile phase. [Embodiment 145] The apparatus according to any one of embodiments 142 to 144, further comprising a cooling device along the recirculation loop between the outlet and the inlet, the cooling device being operably associated with at least one controller configured to control the temperature of the mobile phase. [Embodiment 146] The apparatus according to any one of embodiments 142 to 145, further comprising an oxygenation unit along the recirculation loop between the outlet and the inlet, the oxygenation unit being operably associated with at least one controller configured to control the amount of oxygen provided to the mobile phase. [Embodiment 147] The device according to any one of Embodiments 121 to 146, wherein the member is optically transparent. [Embodiment 148] The device according to any one of Embodiments 121 to 147, wherein the member enables conversion or transmission of energy provided by an energy source selected from the group consisting of electricity, chemistry, magnetism, electromagnetism, photons, acoustics, heating, and combinations thereof. [Embodiment 149] The device according to any one of Embodiments 121 to 148, wherein the polymerizable liquid does not include a dead zone. [Embodiment 150] The device according to any one of Embodiments 122 to 149, wherein the recirculation loop is operably associated with at least one controller configured to maintain a continuous flow of the mobile phase. [Embodiment 151] The device according to any one of Embodiments 121 to 150, configured to provide an energy source to the build region through the member to form a solid polymer from the polymerizable liquid. [Embodiment 152] The device according to any one of Embodiments 121 to 151, wherein the energy source is an optical engine. [Embodiment 153] The device according to Embodiment 152, wherein the optical engine has a light source selected from the group consisting of a mercury light source, an LED light source, halogen light, and a laser. [Embodiment 154] The device according to any one of Embodiments 121 to 153, wherein the energy source is a thermal controller. [Embodiment 155] The device according to any one of Embodiments 121 to 153, wherein the energy source is selected from the group consisting of electricity, chemistry, magnetism, electromagnetism, photons, acoustics, heating, and combinations thereof. [Embodiment 156] The device according to any one of Embodiments 121 to 155, wherein the member is not oxygen permeable.

Claims

**Claim 1** A method of forming a three-dimensional object, comprising: providing an adhesion stage, a member, and a cooling device, wherein the member has a repellent phase thereon, the repellent phase has a build surface, and the adhesion stage and the build surface define a build region therebetween; providing a polymerizable liquid in the build region, wherein the polymerizable liquid is immiscible with the repellent phase; subjecting the polymerizable liquid to polymerization by exposing the build region to energy through at least a portion of the repellent phase to form a solid polymer from the polymerizable liquid, and advancing the adhesion stage away from the build surface to form the three-dimensional object made of the solid polymer; and the method, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface in a vibrating manner. **Claim 2** The method according to claim 1, wherein the cooling device, the member, the repellent phase, or a combination thereof is optically transparent. **Claim 3** The method according to claim 1, wherein the member, the cooling device, the repellent phase, or a combination thereof enables transmission of energy provided by an energy source selected from the group consisting of photons, heating, and combinations thereof. **Claim 4** The method according to claim 1, wherein the repellent phase includes a gel or a liquid. **Claim 5** The method according to claim 1, wherein the polymerizable liquid includes particulate or colloidal materials that can bond together, and the particulate or colloidal materials optionally include metal ions that can deposit to form a bulk metal. **Claim 6** The method according to claim 1, wherein the repellent phase is curved. **Claim 7** The method according to claim 1, wherein the polymerization is carried out by thermal activation. **Claim 8** The method according to claim 1, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a constant speed, a variable speed, or in a vibrating manner, optionally pausing for a fixed period of time, and optionally repeating. **Claim 9** The method according to claim 1, wherein advancing the bonding stage away from the build surface includes advancing the bonding stage away from the build surface at a variable speed.

10. The method according to claim 1, wherein advancing the bonding stage away from the build surface includes advancing the bonding stage a fixed distance away from the build surface at a constant speed, then pausing for a fixed time, and optionally repeating.

11. The method according to claim 1, wherein advancing the bonding stage away from the build surface includes advancing the bonding stage a fixed distance away from the build surface at a variable speed, then pausing for a fixed time, and optionally repeating.

12. The method according to claim 1, wherein advancing the bonding stage away from the build surface in a vibrating manner includes a cycle that includes (i) advancing the bonding stage away from the build surface and (ii) advancing the bonding stage back towards the build surface.

13. The method according to claim 12, further including pausing the bonding stage between advancing the bonding stage away from the build surface and advancing the bonding stage back towards the build surface.

14. The method according to claim 1, further including pausing the bonding stage once after advancing the bonding stage back towards the build surface.

15. The method according to claim 1, wherein the speed of the advancement is from about 0.1 microns per second to about 10,000 microns per second, from about 1 micron per second to about 1,000 microns per second, from about 10 microns per second to about 200 microns per second, or from about 100 microns per second to about 140 microns per second.

16. The method according to claim 1, wherein exposing the build area to energy includes irradiating the build area with an energy source having a fixed energy pattern.

17. The method according to claim 1, wherein exposing the build area to energy includes irradiating the build area with an energy source having a variable energy pattern.

18. The method of claim 17, wherein the variable energy pattern irradiates the build area for from about 0.001 microseconds to about 100 minutes, followed by a short interval of non-irradiation for from about 0.001 microseconds to about 10 seconds, and the irradiation and non-irradiation intervals are optionally repeated.

19. The method of claim 1, wherein the adhesion stage advances at a speed that depends on the energy intensity so as to move away from the build surface.

20. The method of claim 1, wherein printing occurs in all directions.

21. An apparatus for forming a three-dimensional object from a polymerizable liquid, comprising: a support; an adhesion stage operably associated with the support, on which the three-dimensional object is formed; a member having a repelling phase layer thereon, the repelling phase having a build surface, the build surface and the adhesion stage defining a build area therebetween; an optically transparent cooling device; a polymerizable liquid supply operably associated with the build surface and configured to supply a polymerizable liquid into the build area for solidification or polymerization; an energy source configured to deliver energy through the member to the build area to form a solid polymer from the polymerizable liquid; at least one controller operably associated with the energy source to deliver energy to the build area, the at least one controller also being operably associated with the cooling device to cool the build area, and the at least one controller also being operably associated with the adhesion stage to advance the adhesion stage away from the build surface to form the three-dimensional object from the solid polymer; The apparatus, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface in a vibrating manner.

22. The apparatus of claim 21, wherein the member, the repelling phase, the cooling device, or combinations thereof are optically transparent or permit transmission of energy provided by an energy source selected from the group consisting of photons, heating, and combinations thereof.

23. The apparatus of claim 21, wherein the optically transparent cooling device is operably associated with at least one of the member, the rejection phase, and the polymerizable liquid.

24. The apparatus of claim 21, wherein the optically transparent cooling device extends over the entire extent of the build region.

25. The apparatus of claim 21, wherein the at least one controller is operably associated with the optically transparent cooling device and is configured to control the temperature of at least one of the member, the moving phase, or the polymerizable liquid.

26. The apparatus of claim 22, wherein the energy source is configured to provide energy to the build region through the member to form a solid polymer from the polymerizable liquid, and the energy source is selected from the group consisting of photons, heating, and combinations thereof.

27. The apparatus of claim 21, wherein the bonding stage is operably associated with an actuating arm configured to advance the bonding stage away from the build surface.

28. The apparatus of claim 21, wherein advancing the bonding stage away from the build surface includes advancing the bonding stage away from the build surface at a variable speed.

29. The apparatus of claim 21, wherein advancing the bonding stage away from the build surface includes advancing the bonding stage away from the build surface at a constant speed for a fixed distance, then pausing for a fixed time, and optionally repeating.

30. The apparatus of claim 21, wherein advancing the bonding stage away from the build surface includes advancing the bonding stage away from the build surface at a variable speed for a fixed distance, then pausing for a fixed time, and optionally repeating.

31. The apparatus of claim 21, wherein advancing the bonding stage away from the build surface in a vibrating manner includes a cycle that includes (i) advancing the bonding stage away from the build surface and (ii) advancing the bonding stage back towards the build surface.

32. The apparatus according to claim 31, further comprising temporarily stopping the adhesion stage between advancing the adhesion stage away from the build surface and advancing the adhesion stage back to the build surface.

33. The apparatus according to claim 21, further comprising temporarily stopping the adhesion stage once after advancing the adhesion stage back to the build surface.

34. The apparatus according to claim 21, wherein the speed of the advancement is from about 0.1 micron per second to about 10,000 microns per second, from about 1 micron per second to about 1,000 microns per second, from about 10 microns per second to about 200 microns per second, or from about 100 microns per second to about 140 microns per second.

35. The apparatus according to claim 21, wherein exposing the build area to energy includes irradiating the build area with an energy source having a fixed energy pattern.

36. The apparatus according to claim 21, wherein exposing the build area to energy includes irradiating the build area with an energy source having a variable energy pattern.

37. The apparatus according to claim 36, wherein the variable energy pattern includes irradiating the build area for about 0.001 microseconds to about 100 minutes, followed by a short interval of not irradiating for about 0.001 microseconds to about 10 seconds, and optionally repeating the irradiating and non-irradiating intervals.

38. The apparatus according to claim 21, wherein the adhesion stage advances at a speed that depends on the energy intensity away from the build surface.

39. The apparatus according to claim 21, wherein printing occurs in all directions.

40. A method of forming a three-dimensional object, comprising: providing an adhesion stage and a member, wherein the member has a mobile phase thereon, the mobile phase has a build surface, and the adhesion stage and the build surface define a build area therebetween; providing a polymerizable liquid to the build area, wherein the polymerizable liquid is immiscible with the mobile phase. By exposing the build area to energy through at least a portion of the mobile phase, polymerizing the polymerizable liquid to form a solid polymer from the polymerizable liquid, and advancing the adhesion stage away from the build surface to form the three-dimensional object made of the solid polymer, wherein the advancing speed of the adhesion stage is determined by at least one of the geometric shape of the object to be manufactured, data from one or more sensors, or energy intensity, A method, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface in a vibrating manner.

41. The method according to claim 40, wherein the mobile phase includes a moving solid phase, a moving gel phase, a flowing fluid, or a combination thereof.

42. The method according to claim 40, wherein the mobile phase is recycled through a closed loop.

43. The method according to claim 40, further including one or more of filtration, washing, and contamination removal of the mobile phase.

44. The method according to claim 40, further including cooling the mobile phase, and optionally including passing the mobile phase through a cooling device.

45. The method according to claim 44, wherein the cooling device covers the entire range of the build area.

46. The method according to claim 40, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a variable speed.

47. The method according to claim 40, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface by a fixed distance at a constant speed, then pausing for a fixed time, and optionally repeating.

48. The method according to claim 40, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface by a fixed distance at a variable speed, then pausing for a fixed time, and optionally repeating.

49. Advancing the bonding stage away from the build surface in a vibrating manner includes (i) advancing the bonding stage away from the build surface and (ii) advancing the bonding stage back towards the build surface, and includes a cycle, the method according to claim 40.

50. The method according to claim 49, further comprising temporarily stopping the bonding stage between advancing the bonding stage away from the build surface and advancing the bonding stage back towards the build surface.

51. The method according to claim 40, further comprising temporarily stopping the bonding stage once after advancing the bonding stage back towards the build surface.

52. The speed of the advancement is from about 0.1 micron per second to about 10,000 microns per second, from about 1 micron per second to about 1,000 microns per second, from about 10 microns per second to about 200 microns per second, or from about 100 microns per second to about 140 microns per second, the method according to claim 40.

53. Exposing the build area to energy includes irradiating the build area with an energy source having a fixed energy pattern, the method according to claim 40.

54. Exposing the build area to energy includes irradiating the build area with an energy source having a variable energy pattern, the method according to claim 40.

55. The variable energy pattern includes irradiating the build area for about 0.001 microseconds to about 100 minutes, then leaving a short interval of non-irradiation for about 0.001 microseconds to about 10 seconds, and optionally repeating the irradiation and non-irradiation intervals, the method according to claim 54.

56. The bonding stage advances at a speed that depends on the energy intensity away from the build surface, the method according to claim 40.

57. Printing occurs in all directions, the method according to claim 40.

58. An apparatus for forming a three-dimensional object from a polymerizable liquid, comprising a support, and a bonding stage operably associated with the support, on which the three-dimensional object is formed, the bonding stage A member having a layer of mobile phase thereon, wherein the mobile phase has a build surface, and the build surface and the adhesion stage define a build region therebetween, the member; A polymerizable liquid supply unit operably associated with the build surface and configured to supply a polymerizable liquid into the build region for solidification or polymerization; An energy source configured to deliver energy through the member to the build region to form a solid polymer from the polymerizable liquid; At least one controller operably associated with the energy source to deliver energy to the build region, wherein the at least one controller is also operably associated with the adhesion stage to advance the adhesion stage away from the build surface to form the three-dimensional object from the solid polymer, and at least one controller; An apparatus, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface in a vibrating manner.

59. The apparatus according to claim 58, further comprising a cooling device operably associated with at least one of the member, the mobile phase, and the polymerizable liquid, the cooling device being operably associated with at least one controller configured to control the temperature of at least one of the member, the mobile phase, and the polymerizable liquid.

60. The apparatus according to claim 58, wherein the mobile phase includes a moving solid phase, a moving gel phase, a flowing fluid, or a combination of the foregoing.

61. The apparatus according to claim 60, further comprising an outlet in fluid communication with the mobile phase and an inlet in fluid communication with the mobile phase.

62. The apparatus according to claim 61, wherein the outlet is in fluid communication with the inlet to provide a recirculation loop and enable flow of the mobile phase across the membrane.

63. The apparatus according to claim 62, further comprising a filtration unit, a cooling device, or an oxygenation unit provided along the recirculation loop between the outlet and the inlet, wherein the filtration unit, the cooling device, or the oxygenation unit is operably associated with at least one controller configured to filter, clean, or remove contaminants from the mobile phase, control the temperature of the mobile phase, or control the amount of oxygen provided to the mobile phase.

64. The apparatus according to claim 59, wherein the cooling device extends across the build area.

65. The apparatus according to claim 58, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage away from the build surface at a variable speed.

66. The apparatus according to claim 58, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage a fixed distance away from the build surface at a constant speed, then pausing for a fixed time, and optionally repeating.

67. The apparatus according to claim 58, wherein advancing the adhesion stage away from the build surface includes advancing the adhesion stage a fixed distance away from the build surface at a variable speed, then pausing for a fixed time, and optionally repeating.

68. The apparatus according to claim 58, wherein advancing the adhesion stage away from the build surface in a vibratory manner includes a cycle that includes (i) advancing the adhesion stage away from the build surface and (ii) advancing the adhesion stage back towards the build surface.

69. The apparatus according to claim 68, further comprising pausing the adhesion stage between advancing the adhesion stage away from the build surface and advancing the adhesion stage back towards the build surface.

70. The apparatus according to claim 58, further comprising pausing the adhesion stage once after advancing the adhesion stage back towards the build surface.

71. The apparatus according to claim 58, wherein the speed of the advancement is from about 0.1 micron per second to about 10,000 microns per second, from about 1 micron per second to about 1,000 microns per second, from about 10 microns per second to about 200 microns per second, or from about 100 microns per second to about 140 microns per second.

72. The apparatus according to claim 58, wherein exposing the build area to energy includes irradiating the build area with an energy source having a fixed energy pattern.

73. The apparatus according to claim 58, wherein exposing the build area to energy includes irradiating the build area with an energy source having a variable energy pattern.

74. The apparatus according to claim 73, wherein the variable energy pattern includes irradiating the build area for from about 0.001 microseconds to about 100 minutes, followed by a short interval of not irradiating for from about 0.001 microseconds to about 10 seconds, and optionally repeating the irradiating and the non-irradiating intervals.

75. The apparatus according to claim 58, wherein the bonding stage advances at a speed that depends on the energy intensity so as to move away from the build surface.

76. The apparatus according to claim 58, wherein printing occurs in all directions.

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